Process for producing arylsulfur pentafluorides

ABSTRACT

Novel processes for preparing arylsulfur pentafluorides are disclosed. Processes include reacting at least one aryl sulfur compound with a halogen and a fluoro salt to form an arylsulfur halotetrafluoride. The arylsulfur halotetrafluoride is reacted with a fluoride source to form a target arylsulfur pentafluoride.

RELATED APPLICATIONS

This application claims priority to U.S. application Ser. No. 12/053,775entitled “Process for Producing Arylsulfur Pentafluorides”, filed Mar.24, 2008, and to U.S. Patent Application Ser. No. 60/896,669 entitled“Process for Producing Arylsulfur Pentafluorides” filed Mar. 23, 2007,each of which is hereby incorporated by reference in its entirety.

TECHNICAL FIELD

The invention relates to methods and compositions useful in thepreparation of arylsulfur pentafluorides.

BACKGROUND OF THE INVENTION

Arylsulfur pentafluorides compounds are used to introduce one or moresulfur pentafluoride groups into various commercial organic molecules.In particular, arylsulfur pentafluorides have been shown as usefulcompounds (as product or intermediate) in the development of liquidcrystals, in bioactive chemicals such as fungicides, herbicides, andinsecticides, and in other like materials [see Fluorine-containingSynthons (ACS Symposium Series 911), ed by V. A. Soloshonok, AmericanChemical Society (2005), pp. 108-113]. However, as discussed herein,conventional synthetic methodologies to produce arylsulfurpentafluorides have proven difficult and are a concern within the art.

Generally, arylsulfur pentafluorides are synthesized using one of thefollowing synthetic methods: (1) fluorination of diaryl disulfides orarylsulfur trifluoride with AgF₂ [see J. Am. Chem. Soc., Vol. 84 (1962),pp. 3064-3072, and J. Fluorine Chem. Vol. 112 (2001), pp. 287-295]; (2)fluorination of di(nitrophenyl)disulfides, nitrobenzenethiols, ornitrophenylsulfur trifluorides with molecular fluorine (F₂) [seeTetrahedron, Vol. 56 (2000), pp. 3399-3408; Eur. J. Org. Chem., Vol.2005, pp. 3095-3100; and U.S. Pat. No. 5,741,935]; (3) fluorination ofdiaryl disulfides or arenethiols with F₂, CF₃OF, or CF₂(OF)₂ in thepresence or absence of a fluoride source (see US Patent Publication No.2004/0249209 A1); (4) fluorination of diaryl disulfides with XeF₂ [seeJ. Fluorine Chem., Vol. 101 (2000), pp. 279-283]; (5) reaction of1,4-bis(acetoxy)-2-cyclohexene with SF₅Br followed by dehydrobrominationor hydrolysis and then aromatization reactions [see J. Fluorine Chem.,Vol. 125 (2004), pp. 549-552]; (6) reaction of4,5-dichloro-1-cyclohexene with SF₅Cl followed by dehydrochlorination[see Organic Letters, Vol. 6 (2004), pp. 2417-2419 and PCT WO2004/011422 A1]; and (7) reaction of SF₅Cl with acetylene, followed bybromination, dehydrobromination, and reduction with zinc, givingpentafluorosulfanylacetylene, which was then reacted with butadiene,followed by an aromatization reaction at very high temperature [see J.Org. Chem., Vol. 29 (1964), pp. 3567-3570].

Each of the above synthetic methods has one or more drawbacks making iteither impractical (time or yield), overly expensive, and/or overlydangerous to practice. For example, synthesis methods (1) and (4)provide low yields and require expensive reaction agents, e.g., AgF₂ andXeF₂. Methods (2) and (3) require the use of F₂, CF₃OF, or CF₂(OF)₂,each of which is toxic, explosive, and corrosive, and products producedusing these methods are at a relatively low yield. Note that handling ofthese gasses is expensive from the standpoint of the gasses production,storage and use. In addition, synthesis methods that require the use ofF₂, CF₃OF, and/or CF₂(OF)₂ are limited to the production of deactivatedarylsulfur pentafluorides, such as nitrophenylsulfur pentafluorides, dueto their extreme reactivity, which leads to side-reactions such asfluorination of the aromatic rings when not deactivated. Methods (5) and(6) also require expensive reactants, e.g., SF₅Cl or SF₅Br, and havenarrow application because the starting cyclohexene derivatives arelimited. Finally, method (7) requires the expensive reactant SF₅Cl andincludes many reaction steps to reach the arylsulfur pentafluorides(timely and low yield). Therefore, problems with the production methodsfor arylsulfur pentafluorides have made it difficult to prepare thematerial in a safe, cost effective and timely fashion.

Phenylsulfur chlorotetrafluoride, p-methylphenylsulfurchlorotetrafluoride, and p-nitrophenylsulfur chlorotetrafluoride weredetected in the reaction of diphenyl disulfide,bis(p-methylphenyl)disulfide, and bis(p-nitrophenyl)disulfide,respectively, with XeF₂ in the presence of tetraethylammonium chloride(see Can. J. Chem., Vol. 75, pp. 1878-1884). Chemical structures of thechlorotetrafluoride compounds were assigned by analysis of the NMR dataof the reaction mixtures, but these compounds were not isolated.Therefore, the physical properties of the chlorotetrafluorides wereunknown. This synthesis method using XeF₂ was industrially impracticalbecause XeF₂ is overly expensive for large scale production.

The present invention is directed toward overcoming one or more of theproblems discussed above.

SUMMARY OF THE INVENTION

The present invention provides novel processes for the production ofarylsulfur pentafluoride, as represented by formula (I):

Embodiments of the invention include reacting at least one aryl sulfurcompound, having a formula (IIa) or (IIb),

with a halogen selected from the group of chlorine, bromine, iodine andinterhalogens, and a fluoro salt (M⁺F⁻, formula III) to form anarylsulfur halotetrafluoride having a formula (IV):

The arylsulfur halotetrafluoride (formula IV) is reacted with a fluoridesource to form the arylsulfur pentafluoride (formula I).

Embodiments of the present invention also provide processes forproducing an arylsulfur pentafluoride (formula I) by reacting at leastone aryl sulfur compound, having a formula (IIa) or (IIb), with ahalogen selected from the group of chlorine, bromine, iodine andinterhalogens, and a fluoro salt (M⁺F⁻, formula III) to form anarylsulfur halotetrafluoride having a formula (IV):

The arylsulfur halotetrafluoride (formula IV) is reacted with a fluoridesource in the presence of a halogen selected from the group of chlorine,bromine, iodine, and interhalogens to form the arylsulfur pentafluoride(formula I).

Embodiments of the present invention also provide processes forproducing arylsulfur pentafluorides (formula I) by reacting anarylsulfur trifluoride having a formula (V):

with a halogen selected from the group of chlorine, bromine, iodine andinterhalogens, and a fluoro salt (formula III) to form an arylsulfurhalotetrafluoride having a formula (IV):

The arylsulfur halotetrafluoride (formula IV) is reacted with a fluoridesource to form the arylsulfur pentafluoride (formula I).

Embodiments of the present invention also provide processes forproducing arylsulfur pentafluorides (formula I) by reacting anarylsulfur trifluoride having a formula (V):

with a halogen selected from the group of chlorine, bromine, iodine andinterhalogens, and a fluoro salt (formula III) to form an arylsulfurhalotetrafluoride having a formula (IV).

The arylsulfur halotetrafluoride (formula IV) is reacted with a fluoridesource in the presence of a halogen selected from the group of chlorine,bromine, iodine, and interhalogens to form the arylsulfur pentafluoride(formula I).

Embodiments of the present invention further provide processes forproducing arylsulfur halotetrafluoride (formula IV) by reacting at leastone aryl sulfur compound having a formula (IIa) or (IIb) with a halogenselected from a group of chlorine, bromine, iodine and interhalogens,and a fluoro salt having a formula (III) to form an arylsulfurhalotetrafluoride having a formula (IV).

Embodiments of the present invention provide processes for producing anarylsulfur pentafluoride (formula I) by reacting an arylsulfurhalotetrafluoride having a formula (IV) with a fluoride source. In someembodiments the fluoride source has a boiling point of approximately 0°C. or more at 1 atm.

Finally, embodiments of the present invention provides processes forproducing an arylsulfur pentafluoride (formula I) by reacting anarylsulfur halotetrafluoride having a formula (IV) with a fluoridesource in the presence of a halogen selected from the group of chlorine,bromine, iodine, and interhalogens to form the arylsulfur pentafluoride.

In addition, the present invention provides novel arylsulfurchlorotetrafluoride represented by formula (IV′) and fluorinatedarylsulfur pentafluoride represented by formula (I′):

These and various other features as well as advantages whichcharacterize embodiments of the invention will be apparent from areading of the following detailed description and a review of theappended claims.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention provide industrially usefulprocesses for producing arylsulfur pentafluorides, as represented byformula (I). Prepared arylsulfur pentafluorides can be used, for amongother things, to introduce one or more sulfur pentafluoride (SF₅) groupsinto various target organic compounds. Unlike previous methods in theart, the processes of the invention utilize low cost reagents to preparemoderate to excellent yields of arylsulfur pentafluoride compounds.Further, methods of the invention provide a greater degree of overallsafety in comparison to most prior art methodologies (for example theuse of F₂ gas).

A distinction of the present invention is that the processes herein areaccomplished at a low cost as compared to other conventional methods.For example, the reagents to perform Xe based reactions are costprohibitive, whereas the present invention utilizes low cost materials:halogens such as Cl₂, Br₂, and I₂.

Embodiments of the invention include processes which comprise (see forexample Scheme 1, Processes I and II) reacting at least one aryl sulfurcompound having a formula (IIa) or a formula (IIb) with a halogenselected from the group of chlorine, bromine, iodine, and interhalogens,and a fluoro salt having a formula (III), to form an arylsulfurhalotetrafluoride, represented by formula (IV). The arylsulfurhalotetrafluoride is then reacted with a fluoride source to form thearylsulfur pentafluoride having a formula (I).

With regard to formulas (I), (IIa), (IIb), (III), and (IV): substituentsR¹, R², R³, R⁴, and R⁵ each is independently a hydrogen atom; a halogenatom that is a fluorine atom, a chlorine atom, a bromine atom, or aniodine atom; a substituted or unsubstituted alkyl group having from 1 to18 carbon atoms, preferably from 1 to 10 carbon atoms; a substituted orunsubstituted aryl group having from 6 to 30 carbon atoms, preferablyfrom 6 to 15 carbon atoms; a nitro group; a cyano group; a substitutedor unsubstituted alkanesulfonyl group having from 1 to 18 carbon atoms,preferably from 1 to 10 carbon atoms; a substituted or unsubstitutedarenesulfonyl group having from 6 to 30 carbon atoms, preferably from 6to 15 carbon atoms; a substituted or unsubstituted alkoxy group havingfrom 1 to 18 carbon atoms, preferably from 1 to 10 carbon atoms; asubstituted or unsubstituted aryloxy group having from 6 to 30 carbonatoms, preferably from 6 to 15 carbon atoms; a substituted orunsubstituted acyloxy group having from 1 to 18 carbon atom, preferablyfrom 1 to 10 carbon atoms; a substituted or unsubstitutedalkanesulfonyloxy group having from 1 to 18 carbon atom, preferably from1 to 10 carbon atoms; a substituted or unsubstituted arenesulfonyloxygroup having from 6 to 30 carbon atoms, preferably from 6 to 15 carbonatoms; a substituted or unsubstituted alkoxycarbonyl group having 2 to18 carbon atoms, preferably from 2 to 10 carbon atoms; a substituted orunsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms,preferably from 7 to 15 carbons; a substituted carbamoyl group having 2to 18 carbon atoms, preferably from 2 to 10 carbon atoms; a substitutedamino group having 1 to 18 carbon atoms, preferably from 1 to 10 carbonatoms; and a SF₅ group; and R⁶ is a hydrogen atom, a silyl group, ametal atom, an ammonium moiety, a phosphonium moiety, or a halogen atom.

With regard to M, M is a metal atom, an ammonium moiety, or aphosphonium moiety, and with regard to X, X is a chlorine atom, abromine atom, or an iodine atom.

The term “alkyl” as used herein is linear, branched, or cyclic alkyl.The alkyl part of alkanesulfonyl, alkoxy, alkanesulfonyloxy, oralkoxycarbonyl group as used herein is also linear, branched, or cyclicalkyl part. The term “substituted alkyl” as used herein means an alkylmoiety having one or more substituents such as a halogen atom, asubstituted or unsubstituted aryl group, and any other group with orwithout a heteroatom(s) such as an oxygen atom(s), a nitrogen atom(s),and/or a sulfur atom(s), which does not limit reactions of thisinvention.

The term “substituted aryl” as used herein means an aryl moiety havingone or more substituents such as a halogen atom, a substituted orunsubstituted alkyl group, and any other group with or without aheteroatom(s) such as an oxygen atom(s), a nitrogen atom(s), and/or asulfur atom(s), which does not limit reactions of this invention.

The term “substituted alkanesulfonyl” as used herein means analkanesulfonyl moiety having one or more substituents such as a halogenatom, a substituted or unsubstituted aryl group, and any other groupwith or without a heteroatom(s) such as an oxygen atom(s), a nitrogenatom(s), and/or a sulfur atom(s), which does not limit reactions of thisinvention.

The term “substituted arenesulfonyl” as used herein means anarenesulfonyl moiety having one or more substituents such as a halogenatom, a substituted or unsubstituted alkyl group, and any other groupwith or without a heteroatom(s) such as an oxygen atom(s), a nitrogenatom(s), and/or a sulfur atom(s), which does not limit reactions of thisinvention.

The term “substituted alkoxy” as used herein means an alkoxy moietyhaving one or more substituents such as a halogen atom, a substituted orunsubstituted aryl group, and any other group with or without aheteroatom(s) such as an oxygen atom(s), a nitrogen atom(s), and/or asulfur atom(s), which does not limit reactions of this invention.

The term “substituted aryloxy” as used herein means an aryloxy moietyhaving one or more substituents such as a halogen atom, a substituted orunsubstituted alkyl group, and any other group with or without aheteroatom(s) such as an oxygen atom(s), a nitrogen atom(s), and/or asulfur atom(s), which does not limit reactions of this invention.

The term “substituted acyloxy” as used herein means an acyloxy moietyhaving one or more substituents such as a halogen atom, a substituted orunsubstituted alkyl group, a substituted or unsubstituted aryl group,and any other group with or without a heteroatom(s) such as an oxygenatom(s), a nitrogen atom(s), and/or a sulfur atom(s), which does notlimit reactions of this invention.

The term “substituted alkanesulfonyloxy” as used herein means analkanesulfonyloxy moiety having one or more substituents such as ahalogen atom, a substituted or unsubstituted aryl group, and any othergroup with or without a heteroatom(s) such as an oxygen atom(s), anitrogen atom(s), and/or a sulfur atom(s), which does not limitreactions of this invention.

The term “substituted arenesulfonyloxy” as used herein means anarenesulfonyloxy moiety having one or more substituents such as ahalogen atom, a substituted or unsubstituted alkyl group, and any othergroup with or without a heteroatom(s) such as an oxygen atom(s), anitrogen atom(s), and/or a sulfur atom(s), which does not limitreactions of this invention.

The term “substituted alkoxycarbonyl” as used herein means analkoxycarbonyl moiety having one or more substituents such as a halogenatom, a substituted or unsubstituted aryl group, and any other groupwith or without a heteroatom(s) such as an oxygen atom(s), a nitrogenatom(s), and/or a sulfur atom(s), which does not limit reactions of thisinvention.

The term “substituted aryloxycarbonyl” as used herein means anaryloxycarbonyl moiety having one or more substituents such as a halogenatom, a substituted or unsubstituted alkyl group, and any other groupwith or without a heteroatom(s) such as an oxygen atom(s), a nitrogenatom(s), and/or a sulfur atom(s), which does not limit reactions of thisinvention.

The term “substituted carbamoyl” as used herein means a carbamoyl moietyhaving one or more substituents such as a substituted or unsubstitutedalkyl group, a substituted or unsubstituted aryl group, and any othergroup with or without a heteroatom(s) such as an oxygen atom(s), anitrogen atom(s), and/or a sulfur atom(s), which does not limitreactions of this invention.

The term “substituted amino” as used herein means an amino moiety havingone or more substituents such as a substituted or unsubstituted acylgroup, a substituted or unsubstituted alkanesulfonyl group, asubstituted or unsubstituted arenesulfonyl group, and any other groupwith or without a heteroatom(s) such as an oxygen atom(s), a nitrogenatom(s), and/or a sulfur atom(s), which does not limit reactions of thisinvention.

Among the substituents, R¹, R², R³, R⁴, and R⁵, described above, ahydrogen atom, a halogen atom, a substituted or unsubstituted alkylgroup, a substituted or unsubstituted aryl group, a nitro group, a cyanogroup, a substituted or unsubstituted alkanesulfonyl group, asubstituted or unsubstituted arenesulfonyl group, a substituted orunsubstituted alkoxy group, a substituted or unsubstituted aryloxygroup, a substituted or unsubstituted acyloxy group, and a substitutedor unsubstituted alkoxycarbonyl group are preferable, and a hydrogenatom, a halogen atom, a substituted or unsubstituted alkyl group, asubstituted or unsubstituted aryl group, and a nitro group are morepreferable from the viewpoint of availability of the starting materials.

Note that according to the nomenclature of Chemical Abstract Index Name,and in accordance with the present disclosure, for example, C₆H₅—SF₅ isnamed sulfur, pentafluorophenyl-; p-Cl—C₆H₄—SF₅ is named sulfur,(4-chlorophenyl)pentafluoro-; and p-CH₃—C₆H₄—SF₅ is named sulfur,pentafluoro(4-methylphenyl)-. C₆H₅—SF₄Cl is named sulfur,chlorotetrafluorophenyl-; p-CH₃—C₆H₄—SF₄Cl is named sulfur,chlorotetrafluoro(4-methylphenyl)-; and p-NO₂—C₆H₄—SF₄Cl is namedsulfur, chlorotetrafluoro(4-nitrophenyl)-.

Arylsulfur halotetrafluoride compounds of formula (IV) include isomerssuch as trans-isomers and cis-isomers as shown below; arylsulfurhalotetrafluoride is represented by ArSF₄X:

Table 1 provides structure names and formulas for reference whenreviewing Schemes 1, 3˜10 and Examples 1˜34:

TABLE 1 Formulas (I~V) Name Structure/Formula Number Arylsulfurpentafluoride

Aryl sulfur compound

Aryl sulfur compound

Fluoro salt M⁺F⁻ (III) Arylsulfur halotetrafluoride

Arylsulfur trifluoride

Process I (Scheme 1)

Process I includes reacting at least one aryl sulfur compound, having aformula (IIa) or (IIb), with a halogen selected from the group ofchlorine, bromine, iodine and interhalogens, and a fluoro salt (M⁺F⁻,formula III) to form an arylsulfur halotetrafluoride having a formula(IV).

The substituent(s), R¹, R², R³, R⁴, and R⁵, of the products representedby the formula (IV) may be different from the substituent(s), R¹, R²,R³, R⁴, and R⁵, of the starting materials represented by the formulas(IIa) and/or (IIb). Thus, embodiments of this invention includetransformation of the R¹, R², R³, R⁴, and R⁵ to different R¹, R², R³,R⁴, and R⁵ which may take place during the reaction of the presentinvention or under the reaction conditions as long as the —S—S— or—S-moiety is transformed to a —SF₄X group(s).

Illustrative aryl sulfur compounds, as represented by formula (IIa), ofthe invention include, but are not limited to: diphenyl disulfide, eachisomer of bis(fluorophenyl)disulfide, each isomer ofbis(difluorophenyl)disulfide, each isomer ofbis(trifluorophenyl)disulfide, each isomer ofbis(tetrafluorophenyl)disulfide, bis(pentafluorophenyl)disulfide, eachisomer of bis(chlorophenyl)disulfide, each isomer ofbis(dichorophenyl)disulfide, each isomer ofbis(trichlorophenyl)disulfide, each isomer of bis(bromophenyl)disulfide,each isomer of bis(dibromophenyl)disulfide, each isomer ofbis(iodophenyl)disulfide, each isomer ofbis(chlorofluorophenyl)disulfide, each isomer ofbis(bromofluorophenyl)disulfide, each isomer ofbis(bromochlorophenyl)disulfide, each isomer ofbis(fluoroiodophenyl)disulfide, each isomer of bis(tolyl)disulfide, eachisomer of bis[(methoxymethyl)phenyl]disulfide, each isomer ofbis{[(cyclohexyloxy)methyl]phenyl}disulfide, each isomer ofbis[(phenylmethyl)phenyl]disulfide, each isomer ofbis[(cyanomethyl)phenyl]disulfide, each isomer ofbis[(nitromethyl)phenyl]disulfide, each isomer ofbis{[(methanesulfonyl)methyl]phenyl}disulfide, each isomer ofbis{[(benzenesulfonyl)methyl]phenyl}disulfide, each isomer ofbis(ethylphenyl)disulfide, each isomer ofbis[(methoxyethyl)phenyl]disulfide, each isomer ofbis[(nitroethyl)phenyl]disulfide, each isomer ofbis[(phenylethyl)phenyl]disulfide, each isomer ofbis[chloro(methyl)phenyl]disulfide, bis[bromo(methyl)phenyl]disulfide,each isomer of bis[(trifluoromethyl)phenyl]disulfide, each isomer ofbis(dimethylphenyl)disulfide, each isomer ofbis[chloro(dimethyl)phenyl]disulfide, each isomer ofbis[di(trifluoromethyl)phenyl]disulfide, each isomer ofbis(trimethylphenyl)disulfide, each isomer ofbis[chloro(trimethyl)phenyl]disulfide, each isomer ofbis(tetramethylphenyl)disulfide, each isomer ofbis[chloro(tetramethyl)phenyl]disulfide,bis(pentamethylphenyl)disulfide, each isomer ofbis(ethylphenyl)disulfide, each isomer ofbis[(2,2,2-trifluoroethyl)phenyl]disulfide, each isomer ofbis[(perfluoroethyl)phenyl]disulfide, each isomer ofbis(diethylphenyl)disulfide, each isomer ofbis(ethylmethylphenyl)disulfide, each isomer ofbis(propylphenyl)disulfide, each isomer ofbis(isopropylphenyl)disulfide, each isomer of bis(butylphenyl)disulfide,each isomer of bis(sec-butylphenyl)disulfide, each isomer ofbis(isobutylphenyl)disulfide, each isomer ofbis(tert-butylphenyl)disulfide, each isomer ofbis(cyclopropylphenyl)disulfide, each isomer ofbis(cyclopentylphenyl)disulfide, each isomer ofbis(cyclohexylphenyl)disulfide, each isomer ofbis{[(cyclohexyl)cyclohexyl]phenyl}disulfide, each isomer ofbis(biphenyl)disulfide, each isomer of bis(tolylphenyl)disulfide, eachisomer of bis[(chlorophenyl)phenyl]disulfide, each isomer ofbis[(bromophenyl)phenyl]disulfide, each isomer ofbis[(nitrophenyl)phenyl]disulfide, each isomer ofbis(terphenylyl)disulfide, each isomer ofbis[(phenyl)terphenylyl]disulfide, each isomer ofbis[(methanesulfonyl)phenyl]disulfide, each isomer ofbis[(trifluoromethanesulfonyl)phenyl]disulfide, each isomer ofbis[(benzenesulfonyl)phenyl]disulfide, each isomer ofbis[(toluenesulfonyl)phenyl]disulfide, each isomer ofbis(methoxyphenyl)disulfide, each isomer of bis(ethoxyphenyl)disulfide,each isomer of bis(propoxyphenyl)disulfide, each isomer ofbis(butoxyphenyl)disulfide, each isomer ofbis(cyclopropylphenyl)disulfide, bis(cyclohexyloxylphenyl)disulfide,each isomer of bis[(trifluoromethoxy)phenyl]disulfide, each isomer ofbis[(perfluoroethoxyl)phenyl]disulfide, each isomer ofbis[(trifluoroethoxy)phenyl]disulfide, each isomer ofbis[(tetrafluoroethoxy)phenyl]disulfide, each isomer ofbis[(perfluoropropoxy)phenyl]disulfide, each isomer ofbis(phenyloxyphenyl)disulfide, each isomer ofbis(fluorophenyloxyphenyl)disulfide, each isomer ofbis(chlorophenyloxyphenyl)disulfide, each isomer ofbis(bromophenyloxyphenyl)disulfide, each isomer ofbis(nitrophenyloxyphenyl)disulfide, each isomer ofbis[(dinitrophenyloxy)phenyl]disulfide, each isomer ofbis[(pentafluorophenyloxy)phenyl]disulfide, each isomer ofbis(trifluoromethylphenyloxyphenyl)disulfide, each isomer ofbis(cyanophenyloxyphenyl)disulfide, each isomer ofbis(naphthyloxylphenyl)disulfide, each isomer ofbis[(heptafluoronaphthyloxy)phenyl]disulfide, each isomer ofbis[acetoxyphenyl]disulfide, each isomer ofbis[(benzoyloxy)phenyl]disulfide, each isomer ofbis[(methanesulfonyloxy)phenyl]disulfide, each isomer ofbis[(benzenesulfonyloxy)phenyl]disulfide, each isomer ofbis[(toluenesulfonyloxy)phenyl]disulfide, each isomer ofbis[(methoxycarbonyl)phenyl]disulfide, each isomer ofbis[(ethoxycarbonyl)phenyl]disulfide, each isomer ofbis[(phenoxycarbonyl)phenyl]disulfide, each isomer ofbis[(N,N-dimethylcarbamoyl)phenyl]disulfide, each isomer ofbis[(N,N-diethylcarbamoyl)phenyl]disulfide, each isomer ofbis[(N,N-diphenylcarbamoyl)phenyl]disulfide, each isomer ofbis[(N,N-dibenzylcarbamoyl)phenyl]disulfide, each isomer ofbis[(N-acetyl-N-methylamino)phenyl]disulfide, each isomer ofbis[(N-acetyl-N-phenylamino)phenyl]disulfide, each isomer ofbis[(N-acetyl-N-benzylamino)phenyl]disulfide, each isomer ofbis[(N-benzoyl-N-methylamino)phenyl]disulfide, each isomer ofbis[(N-methanesulfonyl-N-methylamino)phenyl]disulfide, each isomer ofbis[(N-toluenesulfonyl-N-methylamino)phenyl]disulfide, each isomer ofbis[(N-toluenesulfonyl-N-benzylamino)phenyl]disulfide, and each isomerof bis[(pentafluorosulfanyl)phenyl]disulfide. Each of the above formula(IIa) compounds is available (see for example Sigma, Acros, TCI,Lancaster, Alfa Aesar, etc.) or can be prepared in accordance withunderstood principles of synthetic chemistry.

Illustrative aryl sulfur compounds, as represented by formula (IIb), ofthe invention include, but are not limited to: benzenethiol, each isomerof fluorobenzenethiol (o-, m-, and p-fluorobenzenethiol), each isomer ofchlorobenzenethiol, each isomer of bromobenzenethiol, each isomer ofiodobenzenethiol, each isomer of difluorobenzenethiol, each isomer oftrifluorobenzenethiol, each isomer of tetrafluorobenzenethiol,pentafluorobenzenethiol, each isomer of dichlorobenzenethiol, eachisomer of chlorofluorobenzenethiol, each isomer of methylbenzenethiol,each isomer of (trifluoromethyl)benzenethiol, each isomer ofdimethylbenzenethiol, each isomer of bis(trifluoromethyl)benzenethiol,each isomer of methyl(trifluoromethyl)benzenethiol, each isomer oftrimethylbenzenethiol, each isomer of tetramethylbenzenethiol,pentamethylbenzenethiol, each isomer of ethylbenzenethiol, each isomerof (2,2,2-trifluoroethyl)benzenethiol, each isomer of(perfluoroethyl)benzenethiol, each isomer of diethylbenzenethiol, eachisomer of ethylmethylbenzenethiol, each isomer of propylbenzenethiol,each isomer of isopropylbenzenethiol, each isomer of butylbenzenethiol,each isomer of sec-butylbenzenethiol, each isomer ofisobutylbenzenethiol, each isomer of tert-butylbenzenethiol, each isomerof nitrobenzenethiol, each isomer of dinitrobenzenethiol, each isomer ofcyanobenzenethiol, each isomer of phenylbenzenethiol, each isomer oftolylbenzenethiol, each isomer of (chlorophenyl)benzenethiol, eachisomer of (bromophenyl)benzenethiol, each isomer of(nitrophenyl)benzenethiol, each isomer of (methanesulfonyl)benzenethiol,each isomer of (trifluoromethanesulfonyl)benzenethiol, each isomer of(benzenesulfonyl)benzenethiol, each isomer of(toluenesulfonyl)benzenethiol, each isomer of(methoxycarbonyl)benzenethiol, each isomer of(ethoxycarbonyl)benzenethiol, each isomer of(phenoxycarbonyl)benzenethiol, each isomer of(N,N-dimethylcarbamoyl)benzenethiol, each isomer of(N,N-diethylcarbamoyl)benzenethiol, each isomer of(N,N-dibenzylcarbamoyl)benzenethiol, each isomer of(N,N-diphenylcarbamoyl)benzenethiol, each isomer of(N-acetyl-N-methylamino)benzenethiol, each isomer of(N-acetyl-N-phenylamino)benzenethiol, each isomer of(N-acetyl-N-benzylamino)benzenethiol, each isomer of(N-benzoyl-N-methylamino)benzenethiol, each isomer of(N-methanesulfonyl-N-methylamino)benzenethiol, each isomer of(N-toluenesulfonyl-N-methylamino)benzenethiol, each isomer of(N-toluenesulfonyl-N-benzylamino)benzenethiol, and each isomer of(pentafluorosulfanyl)benzenethiol; lithium, sodium, and potassium saltsof the benzenethiol compounds exemplified here; ammonium,diethylammonium, triethylammonium, trimethylammnoim,tetramethylammonium, tetraethylammonium, tetrapropylammonium, andtetrabutylammonium salts of the benzenethiol compounds exemplified here;tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium,tetrabutylphosphonium, and tetraphenylphosphonium salts of thebenzenethiol compounds exemplified here; and S-trimethylsilyl,S-triethylsilyl, S-tripropylsilyl, S-dimethyl-t-butylsilyl, andS-dimethylphenylsilyl derivative of the benzenethiol compoundsexemplified here. Examples of aryl sulfur compounds of formula (IIb)where R⁶ is a halogen atom are benzenesulfenyl chloride, each isomer ofnitrobenzenesulfenyl chloride, each isomer of dinitrobenzenesulfenylchloride, and other like compounds. Each of the above formula (IIb)compounds is available (see for example Sigma, Acros, TCI, Lancaster,Alfa Aesar, etc.) or can be prepared in accordance with understoodprinciples of synthetic chemistry.

Typical halogens employable in the present invention include chlorine(Cl₂), bromine (Br₂), iodine (I₂), and interhalogens such as ClF, BrF,ClBr, ClI, Cl₃I, and BrI. Among these, chlorine (Cl₂) is preferable dueto low cost.

Fluoro salts, having a formula (III), are those which are easilyavailable and are exemplified by metal fluorides, ammonium fluorides,and phosphonium fluorides. Examples of suitable metal fluorides arealkali metal fluorides such as lithium fluoride, sodium fluoride,potassium fluoride (including spray-dried potassium fluoride), rubidiumfluoride, and cesium fluoride. Examples of suitable ammonium fluoridesare tetramethylammonium fluoride, tetraethylammonium fluoride,tetrapropylammonium fluoride, tetrabutylammonium fluoride,benzyltrimethylammonium fluoride, benzyltriethylammonium fluoride, andso on. Examples of suitable phosphonium fluorides aretetramethylphosphonium fluoride, tetraethylphosphonium fluoride,tetrapropylphosphonium fluoride, tetrabutylphosphonium fluoride,tetraphenylphosphonium fluoride, tetratolylphosphonium fluoride, and soon. The alkali metal fluorides, such as potassium fluoride and cesiumfluoride, are preferable from the viewpoint of availability and capacityto result in high yield, and potassium fluoride is most preferable fromthe viewpoint of cost.

As a fluoro salt (formula III), there can be used a mixture of a metalfluoride and an ammonium fluoride or a phosphonium fluoride, a mixtureof an ammonium fluoride and a phosphonium fluoride, and a mixture of ametal fluoride, an ammonium fluoride, and a phosphonium fluoride.

As a fluoro salt (formula III), there can also be used a mixture of ametal fluoride and an ammonium salt having an anion part other than F⁻;a mixture of a metal salt having an anion part other than F⁻ and anammonium fluoride; a mixture of a metal fluoride and a phosphonium salthaving an anion part other than F⁻; a mixture of a metal salt having ananion part other than F⁻ and a phosphonium fluoride; a mixture of anammonium fluoride and a phosphonium salt having an anion part other thanF⁻; and a mixture of an ammonium salt having an anion part other than F⁻and a phosphonium fluoride. Furthermore, there can be used a mixture ofa metal fluoride, an ammonium fluoride, and a phosphonium salt having ananion part other than F⁻; a mixture of a metal fluoride, an ammoniumsalt having an anion part other than F⁻, and a phosphonium fluoride; amixture of a metal salt having an anion part other than F⁻, an ammoniumfluoride, and a phosphonium fluoride; a mixture of a metal fluoride, anammonium salt having an anion part other than F⁻, and a phosphonium salthaving an anion part other than F⁻; and so on. These salts can undertakea mutual exchange reaction of the anion parts between and among thesesalts (for example, see Scheme 2).

The combination of these salts may accelerate the reactions in ProcessI, because the reaction may depend on the solubility of the fluoro saltsto the solvent used. As such, a high concentration of fluoride anions(F⁻) will increase the available fluoride anion during the reaction.Therefore, one may choose a suitable combination of these salts in orderto increase the effective concentration of F⁻. The amount (used againstthe amount of the metal fluoride, ammonium fluorides, and/or phosphoniumfluorides) of the metal, ammonium, and phosphonium salts having anionparts other than F⁻ can be chosen from the catalytic amounts to anyamounts that do not interfere with the reactions or do not so decreasethe yields of the products. The anion parts other than F⁻ can be chosenfrom any anions which do not limit the reactions or do not so decreasethe yields of the products. The examples of the anion parts other thanF⁻ are, but are not limited to, Cl⁻, Br⁻, I⁻, BF₄ ⁻, PF₆ ⁻, SO₄ ⁻,⁻OCOCH₃, ⁻OCOCF₃, ⁻OSO₂CH₃, ⁻OSO₂CF₃, ⁻OSO₂C₄F₉, ⁻OSO₂C₆H₅,⁻OSO₂C₆H₄CH₃, ⁻OSO₂C₆H₄Br, and so on. Among them, the anion parts (otherthan F⁻) which do not have an oxygen anion(s) are preferable, and Cl⁻,BF₄ ⁻ and PF₆ ⁻ are more preferable because of high yield reactions. Inaddition, Cl⁻ is most preferable because of the cost.

From the viewpoint of efficiency and yields of the reactions, Process Iis preferably carried out in the presence of one or more solvents. Thesolvent is preferably an inert, polar, aprotic solvent. The preferablesolvents will not substantially react with the starting materials andreagents, the intermediates, and the final products. Suitable solventsinclude, but are not limited to, nitriles, ethers, nitro compounds, andso on, and mixtures thereof. Illustrative nitriles are acetonitrile,propionitrile, benzonitrile, and so on. Illustrative ethers aretetrahydrofuran, diethyl ether, dipropyl ether, dibutyl ether, t-butylmethyl ether, dioxane, glyme, diglyme, triglyme, and so on. Illustrativenitro compounds are nitromethane, nitroethane, nitropropane,nitrobenzene, and so on. Acetonitrile is a preferred solvent for use inProcess I from a viewpoint of providing higher yields of the products.

In order to obtain good yields of product in Process I, the reactiontemperature can be selected in the range of about −60° C.˜+70° C. Morepreferably, the reaction temperature can be selected in the range ofabout −40° C.˜+50° C. Furthermore preferably, the reaction temperaturecan be selected in the range of about −20° C.˜+40° C.

Reaction conditions of Process I are optimized to obtain economicallygood yields of product. In one illustrative embodiment, from about 5 molto about 20 mol of halogen are combined with about 1 mol of aryl sulfurcompound (formula IIa) to obtain a good yield of arylsulfurhalotetrafluorides (formula IV). In another embodiment, from about 3 toabout 12 mol of halogen are combined with 1 mol of aryl sulfur compoundof formula IIb (R⁶=a hydrogen atom, a silyl group, a metal atom, anammonium moiety, or a phosphonium moiety) to obtain good yields ofarylsulfur halotetrafluorides (formula IV). From about 2 to about 8 molof halogen are combined with 1 mol of aryl sulfur compound of formulaIIb (R⁶=a halogen atom) to obtain good yields of arylsulfurhalotetrafluorides (formula IV). The amount of a fluoro salt (formulaIII) used in embodiments of Process I can be in the range of from about8 to about 24 mol against 1 mol of aryl sulfur compound of formula (IIa)to obtain economically good yields of product. The amount of a fluorosalt (formula III) used in embodiments of Process I can be in the rangeof from about 4 to about 12 mol against 1 mol of aryl sulfur compound offormula (IIb) to obtain economically good yields of product.

Note that the reaction time for Process I varies dependent upon reactiontemperature, and the types and amounts of substrates, reagents, andsolvents. As such, reaction time is generally determined as the amountof time required to complete a particular reaction, but can be fromabout 0.5 h to several days, preferably, within a few days.

A more complete reaction mechanism of Process I is shown in Scheme 3above. Aryl sulfur compound of formula (IIa) reacts with halogen to formarylsulfur halide (IIb′=IIb when R⁶=a halogen atom), which then reactswith halogen and fluoro salt (M⁺F⁻) to form arylsulfur trifluoride(formula V). The arylsulfur trifluoride further reacts with halogen andfluoro salt to give the arylsulfur halotetrafluoride (formula (IV)). Assuch, the compounds as represented by formula (V) act as intermediatesin the formation of compounds of formula (IV). The compounds asrepresented by formula (IIb′) also act as intermediates. The startingaryl sulfur compound of formula (IIb when R⁶=a halogen atom) reacts withhalogen and fluoro salt to form the arylsulfur trifluoride. Aryl sulfurcompounds as represented by formula (IIb when R⁶=a hydrogen atom, ametal atom, an ammonium moiety, or a phosphonium moiety) react withhalogen to form aryl sulfur compounds as represented by formula (IIa) orformula (IIb′), which then reacts with halogen and fluoro salt to givethe arylsulfur trifluoride (formula V). As such, the compounds asrepresented by formula (IIa) or (IIb′) act as intermediates in theformation of compounds of formula (IV) from aryl sulfur compounds offormula (IIb, R⁶ except for a halogen atom). The reaction mechanism forthe production of arylsulfur halotetrafluoride (formula IV) viaarylsulfur trifluoride (formula V) was confirmed by ¹⁹F NMR of anintermediate reaction mixture. In addition, the arylsulfur trifluoridecan be converted to the arylsulfur halotetrafluoride (formula IV) underthe similar reaction conditions as demonstrated by at least Example 14.

Process II (Scheme 1)

Embodiments of the invention include Process II: a reaction ofarylsulfur halotetrafluoride, obtained by the process I, with a fluoridesource, as shown in Scheme 1.

The substituent(s), R¹, R², R³, R⁴, and R⁵, of the products representedby the formula (I) may be different from the substituent(s), R¹, R², R³,R⁴, and R⁵, of the materials represented by the formula (IV). Thus,embodiments of this invention include transformation of the R¹, R², R³,R⁴, and R⁵ to different R¹, R², R³, R⁴, and R⁵ which may take placeduring the reaction of the present invention or under the reactionconditions as long as the —SF₄X is transformed to a —SF₅ group.

Fluoride sources employable in Process II are anhydrous compounds thatdisplay fluoride activity to the arylsulfur halotetrafluoride (formulaIV). The fluoride sources can be selected from fluorides of typicalelements in the Periodic Table, fluorides of transition elements in thePeriodic Table, and mixture or compounds between or among thesefluorides of typical elements and/or transition elements. The fluoridesource may be a mixture, salt, or complex with an organic molecule(s)that does (do) not limit the reactions of this invention. The fluoridesources also include mixtures or compounds of fluoride sources withfluoride source-activating compounds such as SbCl₅, AlCl₃, PCl₅, BCl₃,and so on. Process II can be carried out using one or more fluoridesources.

Suitable examples of fluorides of the typical elements include fluoridesof Element 1 in the Periodic Table such as hydrogen fluoride (HF) andalkali metal fluorides, LiF, NaF, KF, RbF, and CsF; fluorides of Element2 (alkaline earth metal fluorides) such as BeF₂, MgF₂, MgFCl, CaF₂,SrF₂, BaF₂ and so on; fluorides of Element 13 such as BF₃, BF₂Cl, BFCl₂,AlF₃, AlF₂Cl, AlFCl₂, GaF₃, InF₃, and so on; fluorides of Element 14such as SiF₄, SiF₃Cl, SiF₂Cl₂, SiFCl₃, GeF₄, GeF₂Cl₂, SnF₄, PbF₂, PbF₄,and so on; fluorides of Element 15 such as PF₅, AsF₅, SbF₃, SbF₅,SbF₄Cl, SbF₃Cl₂, SbF₂Cl₃, SbFCl₄, BiF₅, and so on; fluorides of Element16 such as OF₂, SeF₄, SeF₆, TeF₄, TeF₆, and so on; fluorides of Element17 such as F₂, ClF, ClF₃, BrF, BrF₃, IF₆, and so on.

Suitable examples of fluorides of the transition elements (transitionmeal fluorides) include fluorides of Element 3 in the Periodic Tablesuch as ScF₃, YF₃, LaF₃, and so on; fluorides of Element 4 such as TiF₄,ZrF₃, ZrF₄, HfF₄, and so on; fluorides of Element 5 such as VF₃, VF₅,NbF₅, TaF₅, and so on; fluorides of Element 6 such as CrF₃, MoF₆, WF₆,and so on; fluorides of Element 7 such as MnF₂, MnF₃, ReF₆, and so on;fluorides of Element 8 such as FeF₃, RuF₃, RuF₄, OsF₄, OsF₅, OsF₆, andso on; fluorides of Element 9 such as CoF₂, CoF₃, RhF₃, IrF₆, and so on;fluorides of Element 10 such as NiF₂, PdF₂, PtF₂, PtF₄, PtF₆, and so on;fluorides of Element 11 such as CuF₂, CuFCl, AgF, AgF₂, and so on;fluorides of Element 12 such as ZnF₂, ZnFCl, CdF₂, HgF₂, and so on.

Suitable examples of mixture or compounds between or among the fluoridesof typical elements and/or transition elements include, but are notlimited to, HBF₄ [a compound of hydrogen fluoride (HF) and BF₃], HPF₆,HAsF₆, HSbF₆, LiF/HF [a mixture or salt of lithium fluoride(LiF) andhydrogen fluoride(HF)], NaF/HF, KF/HF, CsF/HF, (CH₃)₄NF/HF,(C₂H₅)₄NF/HF, (C₄H₉)₄NF/HF, ZnF₂/HF, CuF₂/HF, SbF₅/SbF₃, SbF₅/SbF₃/HF,ZnF₂/SbF₅, ZnF₂/SbF₅/HF, KF/SbF₅, KF/SbF₅/HF, and so on.

Suitable examples of mixtures, salts, or complexes of the fluorides withorganic molecules include, but are not limited to, BF₃ diethyl etherate[BF₃.O(C₂H₅)₂], BF₃ dimethyl etherate, BF₃ dibutyl etherate, BF₃tetrahydrofuran complex, BF₃ acetonitrile complex (BF₃.NCCH₃), HBF₄diethyl etherate, HF/pyridine (a mixture of hydrogen fluoride andpyridine), HF/methylpyridine, HF/dimethylpyridine, HF/trimethylpyridine,HF/trimethylamine, HF/triethylamine, HF/dimethyl ether, HF/diethylether, and so on. As HF/pyridine, a mixture of about 70 wt % hydrogenfluoride and about 30 wt % pyridine is preferable because ofavailability.

Among these examples of fluoride sources mentioned above, transitionmetal fluorides, fluorides of the Elements 13˜15, hydrogen fluoride, andmixtures or compounds thereof, and mixtures, salts, or complexes ofthese fluorides with organic molecules are preferable.

Among the transition metal fluorides, the fluorides of Elements 11 (Cu,Ag, Au) and 12 (Zn, Cd, Hg) are exemplified preferably. ZnF₂ and CuF₂are furthermore preferable from the viewpoint of practical operation,yields, and cost. Among the fluorides of the Elements 13˜15, BF₃, AlF₃,AlF₂Cl, SbF₃, SbF₅, SbF₄Cl, and SbF₃Cl₂ are preferably exemplified.Fluorides of Elements 13˜15 can be used preferably for the preparationof polyfluorinated arylsulfur pentafluorides. Among the organicmolecules usable for the mixtures, salts, or complexes with thefluorides, pyridine, ethers such as dimethyl ether, diethyl ether,dipropyl ether, and diisopropyl ether, alkylamines such astrimethylamine and triethylamine, and nitriles such as acetonitrile andpropionitrile are preferable. Among these, pyridine, diethyl ether,triethylamine, and acetonitrile are more preferable because ofavailability and cost.

In some cases, since the reaction of an arylsulfur halotetrafluoride anda fluoride source can be slowed down by flowing an inactive gas such asnitrogen (see Examples 18 and 19), it is not preferable that the vaporon the reaction mixture and/or the gas which may be generated from thereaction mixture be removed, for example by flowing an inactive gas onor through the reaction mixture or other methods. This was an unexpectedfinding discovered by the inventor, as one would not expect removal ofthe reaction vapor to slow the reaction. Therefore, there is a case thatit is preferable that the reaction be carried out in a closed or sealedreactor, by maintaining the reactor at a constant pressure, or byequipping the reactor with a balloon filled with an inactive gas such asnitrogen, or in any other like manner. In this manner, embodiments ofthe invention facilitate the presence of the reaction vapor.

Process II can be carried out with or without a solvent. However, inmany cases, unlike most organic reactions, the present inventiontypically does not require a solvent. This presents an added advantageto performing embodiments of the invention (due to lower cost, nosolvent separating requirements, etc). In some cases, the use of solventis preferable for mild and efficient reactions. Where a solvent isutilized, alkanes, halocarbons, ethers, nitriles, nitro compounds can beused. Example alkanes include normal, branched, cyclic isomers ofpentane, hexane, heptane, octane, nonane, decane, dodecan, undecane, andother like compounds. Illustrative halocarbons include dichloromethane,chloroform, carbon tetrachloride, dichloroethane, trichloroethane,terachloroethane, trichlorotrifluoroethane, chlorobenzene,dichlorobenzene, trichlorobenzene, hexafluorobenzene, benzotrifluoride,bis(trifluoromethyl)benzene, perfluorohexane, perfluorocyclohexane,perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane,perfluorodecalin, and other like compounds. Illustrative ethers includediethyl ether, dipropyl ether, di(isopropyl)ether, dibutyl ether,t-butyl methyl ether, dioxane, glyme (1,2-dimethoxyethane), diglyme,triglyme, and other like compounds. Illustrative nitriles includeacetonitrile, propionitrile, benzonitrile, and other like compounds.Illustrative nitro compounds include nitromethane, nitroethane,nitrobenzene, and other like compounds. Where the fluoride source usedfor the reaction is liquid, it can be used as both a reactant and asolvent. A typical example of this is hydrogen fluoride and a mixture ofhydrogen fluoride and pyridine. Hydrogen fluoride and a mixture ofhydrogen fluoride and pyridine may be usable as a solvent.

In order to optimize yield with regard to Process II, the reactiontemperature is selected in the range of from about −100° C. to about+250° C. More typically, the reaction temperature is selected in therange of from about −80° C. to about +230° C. Most typically, thereaction temperature is selected in the range of from about −60° C. toabout +200° C.

In order to obtain economically good yields of the products, the amountof a fluoride source which provides n number of reactive fluoride(employable for the reaction) per molecule can be selected in the rangeof from about 1/n to about 20/n mol against 1 mol of arylsulfurhalotetrafluoride (see formula IV). More typically, the amount can beselected in the range of from about 1/n to about 10/n mol from theviewpoint of yield and cost, as less amounts of a fluoride sourcedecrease the yield(s) and additional amounts of a fluoride source do notsignificantly improve the yield(s).

As described in Process I, the reaction time of Process II also variesdependent on reaction temperature, the substrates, reagents, solvents,and their amounts used. Therefore, one can modify reaction conditions todetermine the amount of time necessary for completing the reaction ofProcess II, but can be from about 0.1 h to several days, preferably,within a few days.

Embodiments of the invention include processes which comprise (see forexample Scheme 4, Processes I and II′) reacting at least one aryl sulfurcompound having a formula (IIa) or a formula (IIb) with a halogenselected from the group of chlorine, bromine, iodine, and interhalogens,and a fluoro salt having a formula (III), to form an arylsulfurhalotetrafluoride, represented by formula (IV). The arylsulfurhalotetrafluoride is then reacted with a fluoride source in the presenceof a halogen selected from the group of chlorine, bromine, iodine, andinterhalogens to form the arylsulfur pentafluoride as represented by aformula (I).

Process I is as described above.

Process II′ is the same as Process II above except for the followingmodifications: The reaction of an arylsulfur halotetrafluoride and afluoride source can be accelerated by a halogen selected from the groupof chlorine, bromine, iodine, and interhalogens (see Examples 15˜17).

The substituent(s), R¹, R², R³, R⁴, and R⁵, of the products representedby the formula (I) may be different from the substituent(s), R¹, R², R³,R⁴, and R⁵, of the materials represented by the formula (IV). Thus,embodiments of this invention include transformation of the R¹, R², R³,R⁴, and R⁵ to different R¹, R², R³, R⁴, and R⁵ which may take placeduring the reaction of the present invention or under the reactionconditions as long as the —SF₄X is transformed to a —SF₅ group.

The acceleration of the reactions by the presence of a halogen in somecases was an unexpected and surprising finding as discovered by theinventor. While not wanting to be tied to a particular mechanism, it isbelieved that the halogen activates a fluoride source and/or preventsdisproportionation of an arylsulfur halotetrafluoride (formula IV) whichmay occur during this reaction. Therefore, other fluoridesource-activating and/or disproportionation-preventing compounds arewithin the scope of the invention. The reaction in the presence of thehalogen may be carried out by methods such as by adding a halogen to thereaction mixture, dissolving a halogen in the reaction mixture, flowinga halogen gas or vapor into the reaction mixture or the reactor, orothers like means. Among the halogens, chlorine (Cl₂) is preferablebecause of cost.

The amount of halogen is from a catalytic amount to an amount in largeexcess. From the viewpoint of cost, a catalytic amount to 5 mol of thehalogen, can be preferably selected against 1 mol of arylsulfurhalotetrafluoride (formula IV).

Embodiments of the present invention include a process (Process III)which comprises reacting an arylsulfur trifluoride having a formula (V)with a halogen (chlorine, bromine, iodine, or interhalogens) and afluoro salt having a formula (III) to form an arylsulfurhalotetrafluoride having a formula (IV) and (Process II) reacting theobtained arylsulfur halotetrafluoride with a fluoride source to form thearylsulfur pentafluoride having a formula (I). Scheme 5 showingProcesses III and II are shown as follows:

With regard to formulas (I), (III), (IV), and (V), R¹, R², R³, R⁴, R⁵,R⁶, M and X have the same meaning as defined above.

Process III (Scheme 5)

Embodiments of the present invention provide processes for producingarylsulfur pentafluorides (formula I) by reacting an arylsulfurtrifluoride having a formula (V) with a halogen selected from the groupof chlorine, bromine, iodine, and interhalogens and a fluoro salt(formula III) to form an arylsulfur halotetrafluoride having a formula(IV).

The substituent(s), R¹, R², R³, R⁴, and R⁵, of the products representedby the formula (IV) may be different from the substituent(s), R¹, R²,R³, R⁴, and R⁵, of the starting materials represented by the formula(V). Thus, embodiments of this invention include transformation of theR¹, R², R³, R⁴, and R⁵ to different R¹, R², R³, R⁴, and R⁵ which maytake place during the reaction of the present invention or under thereaction conditions as long as the —SF₃ is transformed to a —SF₄X.

Illustrative arylsulfur trifluorides, as represented by formula (V), ofthe invention can be prepared as described in the literature [see J. Am.Chem. Soc., Vol. 84 (1962), pp. 3064-3072, and Synthetic Communication.Vol. 33 (2003), pp. 2505-2509] and are exemplified, but are not limited,by phenylsulfur trifluoride, each isomer of fluorophenylsulfurtrifluoride, each isomer of difluorophenylsulfur trifluoride, eachisomer of trifluorophenylsulfur trifluoride, each isomer oftetrafluorophenylsulfur trifluoride, pentafluorophenylsulfurtrifluoride, each isomer of chlorophenylsulfur trifluoride, each isomerof bromophenylsulfur trifluoride, each isomer ofchlorofluorophenylsulfur trifluoride, each isomer ofbromofluorophenylsulfur trifluoride, each isomer of tolylsulfurtrifluoride, each isomer of chloro(methyl)phenylsulfur trifluoride, eachisomer of dimethylphenylsulfur trifluoride, each isomer ofchloro(dimethyl)phenylsulfur trifluoride, each isomer oftrimethylphenylsulfur trifluoride, each isomer of ethylphenylsulfurtrifluoride, each isomer of propylphenylsulfur trifluoride, each isomerof butylphenylsulfur trifluoride, each isomer of nitrophenylsulfurtrifluoride, each isomer of dinitrophenylsulfur trifluoride, and so on.

As mentioned in the reaction mechanism for the Process I, arylsulfurtrifluorides (formula V) can be the intermediates in the Process I.

A halogen employable in the present invention for Process III is thesame as for Process I described above except for the amount used for thereaction.

Fluoro salts having a formula (III) for Process III are the same as forProcess I described above except for the amount used in the reaction.

It is preferable that the reaction of Process III be carried out using asolvent. Examples of suitable solvents are the same as for Process Idescribed above.

In order to economically get good yields of the products, the reactiontemperature for Process III can be selected in the range of −60° C.˜+70°C. More preferably, the temperature can be selected in the range of −40°C.˜+50° C. Furthermore preferably, the temperature can be selected inthe range of −20° C.˜+40° C.

In order to get good economic yields of product, the amount of a halogenused can be preferably selected in the range of from about 1 to about 5mol, more preferably from about 1 to about 3 mol, against 1 mol ofarylsulfur trifluoride (V).

In order to get good economic yield of the products, the amount offluoro salt (III) used can be preferably selected in the range of about1 to about 5 mol against 1 mol of arylsulfur trifluoride (V).

The reaction time for Process III is dependent on reaction temperature,the substrates, reagents, solvents, and their amounts used. Therefore,one can choose the time necessary for completing each reaction based onmodification of the above parameters, but can be from about 0.5 h toseveral days, preferably, within a few days.

Process II is as described above.

Embodiments of the present invention include a process (Process III)which comprises reacting an arylsulfur trifluoride having a formula (V)with a halogen (chlorine, bromine, iodine, or interhalogens) and afluoro salt having a formula (III) to form an arylsulfurhalotetrafluoride having a formula (IV) and (Process II′) reacting theobtained arylsulfur halotetrafluoride with a fluoride source in thepresence of a halogen selected from the group of chlorine, bromine,iodine, and interhalogens to form the arylsulfur pentafluoride having aformula (I). Scheme 6 showing Processes III and II′ are shown asfollows:

With regard to formulas (I), (III), (IV), and (V), R¹, R², R³, R⁴, R⁵,R⁶, M and X have the same meaning as defined above.

Processes III and II′ are as described above.

Furthermore, the present invention includes a process (Scheme 7, ProcessI) for preparing an arylsulfur halotetrafluoride having a formula (IV),which comprises reacting at least one aryl sulfur compound having aformula (IIa) or a formula (IIb) with a halogen selected from the groupof chlorine, bromine, iodine, and interhalogens and a fluoro salt havinga formula (III) to form the arylsulfur halotetrafluoride.

In the formulas (IIa), (IIb), (III), and (IV), R¹, R², R³, R⁴, R⁵, R⁶, Mand X represent the same meaning as defined above.

Process I is described above.

Furthermore, the present invention includes a process (Scheme 8, ProcessIII) for preparing an arylsulfur halotetrafluoride having a formula(IV), which comprises reacting an arylsulfur trifluoride having aformula (V) with a halogen selected from the group of chlorine, bromine,iodine, and interhalogens and a fluoro salt having a formula (III) toform the arylsulfur halotetrafluoride.

In the formulas (III), (IV), and (V), R¹, R², R³, R⁴, R⁵, M and Xrepresent the same meaning as defined above.

Process III is as described above.

Furthermore, the present invention includes a process (Scheme 9, ProcessII″) for preparing an arylsulfur pentafluoride having a formula (I),which comprises reacting an arylsulfur halotetrafluoride having aformula (IV) with a fluoride source whose boiling point is approximately0° C. or more to form the arylsulfur pentafluoride.

In the formulas (I) and (IV), R¹, R², R³, R⁴, R⁵, and X represent thesame meaning as defined above.

Process II″ (Scheme 9) Process II″ is a reaction of arylsulfurhalotetrafluoride having a formula (IV) with a fluoride source whoseboiling point is approximately 0° C. or more at 1 atm, as shown inScheme 9.

The substituent(s), R¹, R², R³, R⁴, and R⁵, of the products representedby the formula (I) may be different from the substituent(s), R¹, R², R³,R⁴, and R⁵, of the starting materials represented by the formula (IV).Thus, embodiments of this invention include transformation of the R¹,R², R³, R⁴, and R⁵ to different R¹, R², R³, R⁴, and R⁵ which may takeplace during the reaction of the present invention or under the reactionconditions as long as the —SF₄X is transformed to a —SF₅ group.

Process II″ is the same as Process II described above, and, the fluoridesources employable in Process II″ are the same as the fluoride sourcespreviously discussed with reference to Process II, with exception thatProcess II″ fluoride sources have boiling points equal to or above 0° C.at 1 atm.

Furthermore, the present invention includes a process (Scheme 10,Process II′) for preparing an arylsulfur pentafluoride having a formula(I), which comprises reacting an arylsulfur halotetrafluoride having aformula (IV) with a fluoride source in the presence of a halogenselected from the group of chlorine, bromine, iodine, and interhalogensto form the aryl sulfurpentafluoride.

For formulas (I) and (IV), R¹, R², R³, R⁴, R⁵, and X represent the samemeaning as defined above.

Process II′ is as described above.

According to the present invention, the arylsulfur pentafluorides havingthe formula (I) can be easily and cost-effectively produced from easilyavailable starting materials.

The present invention provides novel arylsulfur chlorotetrafluoridesrepresented by formula (IV′) as useful intermediates;

wherein R^(1′), R^(2′), R^(3′), R^(4′), and R^(5′) each is independentlya hydrogen atom, a halogen atom, a linear or branched alkyl group havingone to four carbon atoms, or a nitro group; and where, when R^(3′) is ahydrogen atom, a methyl group, or a nitro group, at least one of R^(1′),R^(2′), R^(4′), and R^(5′) is a halogen atom, a linear or branched alkylgroup having one to four carbon atoms, or a nitro group. The halogenatom here is a fluorine atom, a chlorine atom, a bromine atom, or aniodine atom.

Among these, each isomer of tert-butylphenylsulfur chlorotetrafluoride,each isomer of fluorophenylsulfur chlorotetrafluoride, each isomer ofchlorophenylsulfur chlorotetrafluoride, each isomer of bromophenylsulfurchlorotetrafluoride, each isomer of difluorophenylsulfurchlorotetrafluoride, each isomer of trifluorophenylsulfurchlorotetrafluoride, and 2,3,4,5,6-pentafluorophenylsulfurchlorotetrafluoride are preferable, and 4-tert-butylphenylsulfurchlorotetrafluoride, 4-fluorophenylsulfur chlorotetrafluoride,2-fluorophenylsulfur chlorotetrafluoride, 4-chlorophenylsulfurchlorotetrafluoride, 4-bromophenylsulfur chlorotetrafluoride,3-bromophenylsulfur chlorotetrafluoride, 2,6-difluorophenylsulfurchlorotetrafluoride, 2,4,6-trifluorophenylsulfur chlorotetrafluoride,and 2,3,4,5,6-pentafluorophenylsulfur chlorotetrafluoride are morepreferable.

The present invention also provides novel and useful fluorinatedarylsulfur pentafluorides represented by formula (I′);

wherein at least one of R^(2″), R^(3″), and R^(4″) are a halogen atomand the remainders are a hydrogen atom. The halogen atom here is afluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Among these, 2,3,4,5,6-pentafluorophenylsulfur pentafluoride,2,4,6-trifluorophenylsulfur pentafluoride,3-chloro-2,4,6-trifluorophenylsulfur pentafluoride, and3-chloro-2,6-difluorophenylsulfur pentafluoride are preferable.

The following examples will illustrate the present invention in moredetail, but it should be understood that the present invention is notdeemed to be limited thereto.

EXAMPLES

The following examples are provided for illustrative purposes only andare not intended to limit the scope of the invention. Table 2 providesstructure names and formulas for reference when reviewing the followingexamples:

TABLE 2 Arylsulfur Halotetrafluorides (Formulas Ia, b, d-n and IVa-j, l,n): Formula Number Name Structure Ia Phenylsulfur pentafluoride

Ib p-Methylphenylsulfur pentafluoride

Id p-Fluorophenylsulfur pentafluoride

Ie o-Fluorophenylsulfur pentafluoride

If p-Chlorophenylsulfur pentafluoride

Ig p-Bromophenylsulfur pentafluoride

Ih m-Bromophenylsulfur pentafluoride

Ii p-Nitrophenylsulfur pentafluoride

Ij 2,6-Difluorophenylsulfur pentafluoride

Ik 3-Chloro-2,6- difluorophenylsulfur pentafluoride

Il 2,4,6-Trifluorophenylsulfur pentafluoride

Im 3-Chloro-2,4,6- trifluorophenylsulfur pentafluoride

In 2,3,4,5,6- Pentafluorophenylsulfur pentafluoride

IVa Phenylsulfur chlorotetrafluoride

IVb p-Methylphenylsulfur chlorotetrafluoride

IVe p-(tert-Butyl)phenylsulfur chlorotetrafluoride

IVd p-Fluorophenylsulfur chlorotetrafluoride

IVe o-Fluorophenylsulfur chlorotetrafluoride

IVf p-Chlorophenylsulfur chlorotetrafluoride

IVg p-Bromophenylsulfur chlorotetrafluoride

IVh m-Bromophenylsulfur chlorotetrafluoride

IVi p-Nitrophenylsulfur chlorotetrafluoride

IVj 2,6-Difluorophenylsulfur chlorotetrafluoride

IVl 2,4,6-Trifluorophenylsulfur chlorotetrafluoride

IVn 2,3,4,5,6- Pentafluorophenylsulfur chlorotetrafluoride

Example 1 Synthesis of Phenylsulfur Pentafluoride from DiphenylDisulfide

(Process I) A 500 mL round bottom glassware flask was charged withdiphenyl disulfide (33.0 g, 0.15 mol), dry KF (140 g, 2.4 mol) and 300mL of dry CH₃CN. The stirred reaction mixture was cooled on an ice/waterbath under a flow of N₂ (18 mL/min). After N₂ was stopped, chlorine(Cl₂) was bubbled into a reaction mixture at the rate of about 70mL/min. The Cl₂ bubbling took about 6.5 h. The total amount of Cl₂ usedwas about 1.2 mol. After Cl₂ was stopped, the reaction mixture wasstirred for additional 3 h. N₂ was then bubbled through for 2 hours toremove an excess of Cl₂. The reaction mixture was then filtered with 100mL of dry hexanes in air. About 1 g of dry KF was added to the filtrate.The KF restrains possible decomposition of the product. The filtrate wasevaporated under vacuum and the resulting residue was distilled atreduced pressure to give a colorless liquid (58.0 g, 88%) ofphenylsulfur chlorotetrafluoride: b.p. 80° C./20 mmHg; ¹H NMR (CD₃CN)7.79-7.75 (m, 2H, aromatic), 7.53-7.49 (m, 3H, aromatic); ¹⁹F NMR(CD₃CN) 136.7 (s, SF₄Cl). The NMR analysis showed phenylsulfurchlorotetrafluoride obtained is a trans isomer.

(Process II) A 100 mL fluoropolymer (TEFLON®•PFA) vessel was chargedwith PhSF₄Cl (44 g, 0.2 mol) and dry ZnF₂ (12.3 g, 0.12 mol) in a drybox filled with N₂. The vessel was then equipped with a condenser madeof fluoropolymer and a balloon filled with N₂. The reaction mixture wasslowly heated to 120° C. over a period of one hour. The reaction mixturechanged from colorless to yellow, pink, and then eventually green. Thereaction mixture was stirred at 120° C. for 20 h. After being cooled toroom temperature, about 50 mL of pentane was added to the reactionmixture. The mixture was filtered to remove all insoluble solid to givea yellow solution, which was concentrated. The resulting residue wasdistilled at reduced pressure to give 30.6 g (75%) of phenylsulfurpentafluoride; b.p. 70-71° C./120 mmHg; ¹H NMR (CDCl₃) 7.77-7.74 (m, 2H,aromatic), 7.60-7.40 (m, 3H, aromatic); ¹⁹F NMR (CDCl₃) 85.20-84.13 (m,1F, SF₅), 62.91 (d, 4F, SF₅).

Examples 2-10 Synthesis of Arylsulfur Pentafluorides (I) from ArylSulfur Compounds (IIa)

Substituted arylsulfur pentafluorides (I) were synthesized from thecorresponding aryl sulfur compounds (IIa) by the similar procedure as inExample 1. Table 3 shows the synthesis of the substituted arylsulfurpentafluorides. Table 3 also shows the starting materials and otherchemicals necessary for the Processes I and II, solvents, reactionconditions, and the results, together with those of Example 1. FC-72(Fluorinert®) was used as a solvent in Process II in Examples 9 and 10.The Fluorinert® FC-72 was a perfluorinated organic compound having aboiling point of 56° C., which was a product made by 3M Company.

TABLE 3 Production of Arylsulfur pentafluorides (I) from Aryl sulfurcompounds (IIa) Process II Process I Amount Fluoride Ex. (IIa) Halogen(III) Solvent Conditions (IV) Yield of (IV) source Solv. Conditions (I)Yield 1

Cl₂ ~1.2 mol KF 140 g (2.4 mol) CH₃CH 300 ml 0~5° C. ~9.5 h

88% 44 g (0.2 mol) ZnF₂ 12.3 g (0.12 mol) non 120° C. 20 h

75% 2

Cl₂ 0.73 mol KF 464 g (8 mol) CH₃CN 1 L 0° C. 10.5 h

73% 32 g (137 mmol) ZnF₂ 8.47 g (82 mmol) non 90° C. overnight

71% 3

Cl₂ 0.28 mol KF 36 g (0.63 mol) CH₃CN 100 mL 0~5° C. 2.5 h and r.t.overnight

67% 10 g (42 mmol) ZnF₂ 2.6 g (25 mmol) non 120° C. 16 h

62% 4

Cl₂ 0.31 mol KF 36.5 g (0.63 mol) CH₃CN 100 mL 0~5° C. 1.8 h and r.t.overnight

80% 10 g (42 mmol) ZnF₂ 2.59 g (25 mmol) non 120° C. 15 h

59% 5

Cl₂ 0.72 mol KF 94 g (1.6 mol) CH₃CN 200 mL 0~5° C. 4.5 h and r.t.overnight

77% 30 g 100 mmol) ZnF₂ 6.18 g (60 mmol) heptane 20 mL reflux 17 h

79% 6

Cl₂ 0.88 mmol KF 118 g (2.0 mol) CH₃CN 250 mL 0~5° C. 5.5 h and r.t.overnight

86% 10 g (33 mmol) ZnF₂ 2.0 g (20 mmol) non 120° C. 15 h

78% 7

Cl₂ 0.72 mol KF 94 g (1.6 mol) CH₃CN 200 mL 0~5° C. 4.5 h and r.t.overnight

60% 26.5 g (100 mmol) ZnF₂ 6.18 g (60 mmol) non 150° C. 72 h

36% 8

Cl₂ ~1.02 mol CsF 279 g (1.83 mol) CH₃CN 200 mL 0~5° C. 5 h and r.t.overnight

82% 41.87 g (0.16 mol) ZnF₂ 18.1 g (0.17 mol) non 130° C. 4 h and 180°C. 6h

52% 9

Cl₂ ~1.08 mol KF 90 g (1.55 mol) CH₃CN 300 mL 0~5° C. 6 h and r.t.overnight

67% 4.09 g (14.9 mmol) SbF₅ 0.5~0.6 mL (~8 mmol) FC-72 20 mL r.t. 2 h

60%

20% 10

Cl₂ ~1 mol KF 82 g (1.41 mol) CH₃CN 300 mL 0~5° C. 5 h and r.t.overnight

86% 9.47 g (30.5 mmol) SbF₅ 3.41 g (30.5 mmol) FC-72 40 mL r.t. 2 h

60%

The properties and spectral data of the products, (IV) and (I), obtainedby Examples 2-10 are shown by the following:

p-Methylphenylsulfur chlorotetrafluoride; b.p. 74-75° C./5 mmHg; ¹H NMR(CD₃CN) 7.65 (d, 2H, aromatic), 7.29 (d, 2H, aromatic), 2.36 (s, 3H,CH₃); ¹⁹F NMR (CD₃CN) 137.66 (s, SF₄Cl); High resolution mass spectrum;found 235.986234 (34.9%) (calcd for C₇H₇F₄S³⁷Cl; 235.986363), found233.989763 (75.6%) (calcd for C₇H₇F₄S³⁵Cl; 233.989313). The NMR showsthat p-methylphenylsulfur chlorotetrafluoride obtained is a transisomer.

p-Methylphenylsulfur pentafluoride; b.p. 95-96° C./80 mmHg; ¹H NMR(CDCl₃) 7.63 (d, 2H, aromatic), 7.24 (d, 2H, aromatic), 2.40 (s, 3H,CH₃); ¹⁹F NMR (CDCl₃) 86.55-84.96 (m, 1F, SF), 63.26 (d, 4F, SF₄).

p-Fluorophenylsulfur chlorotetrafluoride; b.p. 60° C./8 mmHg; ¹H NMR(CD₃CN) 7.85-7.78 (m, 2H, aromatic), 7.25-7.15 (m, 2H, aromatic); ¹⁹FNMR (CD₃CN) 137.6 (s, SF₄Cl), −108.3 (s, CF); High resolution massspectrum; found 239.961355 (37.4%) (calcd for C₆H₄F₅S³⁷Cl; 239.961291),found 237.964201 (100%) (calcd for C₆H₄F₅S³⁵Cl; 237.964241). The NMRshows that p-fluorophenylsulfur chlorotetrafluoride obtained is a transisomer.

p-Fluorophenylsulfur pentafluoride; b.p. 71° C./80 mmHg; ¹H NMR (CDCl₃)7.80-7.73 (m, 2H, aromatic), 7.17-7.09 (m, 2H, aromatic); ¹⁹F NMR(CDCl₃) 87.78-83.17 (m, 1F, SF), 63.81 (d, 4F, SF₄), −107.06 (s, 1F,CF); GC-MS m/z 222 (M⁺).

o-Fluorophenylsulfur chlorotetrafluoride; b.p. 96-97° C./20 mmHg; ¹H NMR(CD₃CN) 7.77-7.72 (m, 1H, aromatic), 7.60-7.40 (m, 1H, aromatic),7.25-7.10 (m, 2H, aromatic); ¹⁹F NMR (CD₃CN) 140.9 (d, SF₄Cl), −107.6(s, CF); High resolution mass spectrum; found 239.961474 (25.4%) (calcdfor C₆H₄F₅S³⁷Cl; 239.961291), found 237.964375 (69.8%) (calcd forC₆H₄F₅S³⁵Cl; 237.964241). The NMR shows that o-fluorophenylsulfurchlorotetrafluoride obtained is a trans isomer.

o-Fluorophenylsulfur pentafluoride; b.p. 91-94° C./120 mmHg; ¹H NMR(CDCl₃) 7.78-7.73 (m, 1H, aromatic), 7.55-7.48 (m, 1H, aromatic),7.27-7.17 (m, 2H, aromatic); ¹⁹F NMR (CDCl₃) 82.38-81.00 (m, 1F, SF),68.10 (dd, 4F, SF₄), −108.07 (−108.35) (m, 1F, CF).

p-Bromophenylsulfur chlorotetrafluoride (X); m.p. 58-59° C.; ¹H NMR(CD₃CN) δ 7.67 (s, 4H, aromatic); ¹⁹F NMR (CD₃CN) δ 136.56 (s, SF₄Cl);High resolution mass spectrum; found 301.877066 (16.5%) (calcd for C₆H₄⁸¹Br³⁷ClF₄S; 301.879178), found 299.880655 (76.6%) (calcd for C₆H₄⁸¹Br³⁵ClF₄S; 299.881224 and calcd for C₆H₄ ⁷⁹Br³⁷ClF₄S; 299.882128),found 297.882761 (77.4%) (calcd for C₆H₄ ⁷⁹Br³⁵ClF₄S; 297.884174).Elemental analysis; calcd for C₆H₄BrClF₄S; C, 24.06%; H, 1.35%. Found,C, 24.37%; H, 1.54%. The NMR showed that p-bromophenylsulfurchlorotetrafluoride was obtained as a trans isomer.

p-Bromophenylsulfur pentafluoride; b.p. 77-78° C./10 mmHg; ¹H NMR(CDCl₃) 7.63 (s, 4H, aromatic); ¹⁹F NMR (CDCl₃) 84.13-82.53 (m, 1F, SF),63.11 (d, 4F, SF₄).

m-Bromophenylsulfur chlorotetrafluoride; b.p. 57-59° C./0.8 mmHg; ¹H NMR(CD₃CN) 7.90-7.88 (m, 1H, aromatic), 7.70-7.50 (m, 2H, aromatic),7.40-7.30 (m, 1H, aromatic); ¹⁹F NMR (CD₃CN) 136.74 (s, SF₄Cl). Highresolution mass spectrum; found 301.878031 (29.1%) (calcd for C₆H₄⁸¹Br³⁷ClF₄S; 301.879178), found 299.881066 (100%) (calcd for C₆H₄⁸¹Br³⁵ClF₄S; 299.881224 and calcd for C₆H₄ ⁷⁹Br³⁷ClF₄S; 299.882128),found 297.883275 (77.4%) (calcd for C₆H₄ ⁷⁹Br³⁵ClF₄S; 297.884174). TheNMR showed that m-bromophenylsulfur chlorotetrafluoride obtained was atrans isomer.

m-Bromophenylsulfur pentafluoride; b.p. 69-70° C./10 mmHg; ¹H NMR(CDCl₃) 7.91 (t, 1H, aromatic), 7.72-7.64 (m, 2H, aromatic), 7.35 (t,1H, aromatic); ¹⁹F NMR (CDCl₃) 83.55-82.47 (m, 1F, SF), 63.13 (d, 4F,SF₄).

p-Nitrophenylsulfur chlorotetrafluoride; m.p. 130-131° C.; ¹H NMR(CD₃CN) 8.29 (d, J=7.8 Hz, 2H, aromatic), 8.02 (d, J=7.8 Hz, 2H,aromatic); ¹⁹F NMR (CD₃CN) 134.96 (s, SF₄Cl); High resolution massspectrum; found 266.956490 (38.4%) (calcd for C₆H₄ ³⁷ClF₄NO₂S;266.955791), found 264.959223 (100%) (calcd for C₆H₄ ³⁵ClF₄NO₂S;264.958741). Elemental analysis; calcd for C₆H₄ClF₄NO₂S; C, 27.13%; H,1.52%; N, 5.27%. Found, C, 27.16%; H, 1.74%; N, 4.91%. The NMR showsthat p-nitrophenylsulfur chlorotetrafluoride obtained is a trans isomer.

p-Nitrophenylsulfur pentafluoride; b.p. 74-76° C./3 mmHg; ¹H NMR (CDCl₃)8.36-8.30 (m, 2H, aromatic), 7.99-7.95 (m, 2H, aromatic); ¹⁹F NMR(CDCl₃) 82.32-80.69 (m, 1F, SF), 62.76 (d, 4F, SF₄).

2,6-Difluorophenylsulfur chlorotetrafluoride: The product (b.p. 120-122°C./95-100 mmHg) obtained from Example 8 is a 6:1 mixture of trans- andcis-isomers of 2,6-difluorophenylsulfur chlorotetrafluoride. Thetrans-isomer was isolated as pure form by crystallization; mp.47.6-48.3° C.; ¹⁹F NMR (CDCl₃) δ 143.9 (t, J=26.0 Hz, 4F, SF₄), −104.1(quintet, J=26.0 Hz, 2F, 2,6-F): ¹H NMR (CDCl₃) δ 6.97-7.09 (m, 2H,3,5-H), 7.43-7.55 (m, 1H, 4-H); ¹³C NMR (CDCl₃) δ 157.20 (d, J=262.3Hz), 133.74 (t, J=11.6 Hz), 130.60 (m), 113.46 (d, J=14.6 Hz); highresolution mass spectrum; found 257.950876 (37.6%) (calcd for C₆H₃³⁷ClF₆S; 257.951869), found 255.955740 (100%) (calcd for C₆H₃ ³⁵ClF₆S;255.954819); elemental analysis; calcd for C₆H₃ClF₆S; C, 28.08%, H,1.18%; found; C, 28.24%, H, 1.24%. The cis-isomer was assigned in thefollowing; ¹⁹F NMR (CDCl₃) δ 158.2 (quartet, J=161.8 Hz, 1F, SF), 121.9(m, 2F, SF₂), 76.0 (m, 1F, SF). The ¹⁹F NMR assignment of aromaticfluorine atoms of the cis-isomer could not be done because of possibleoverlapping of the peaks of the trans-isomer.

2,6-Difluorophenylsulfur pentafluoride: m.p. 40.3-41.1° C.; ¹H NMR(CDCl₃) δ 7.51 (m, 1H), 7.04 (m, 2H); ¹⁹F NMR (CDCl₃) 82.32-80.69 (m,1F, SF), 62.76 (d, 4F, SF₄); high resolution mass spectrum; found239.984509 (calcd for C₆H₃F₇S; 239.984370); elemental analysis, calcdfor C₆H₃F₇S; C, 30.01%, H, 1.26%. Found, C, 30.20%, H, 1.47%.

2,4,6-Trifluorophenylsulfur chlorotetrafluoride: trans-isomer; m.p.55.8-56.7° C.; ¹⁹F NMR (CDCl₃) δ 144.07 (t, J=26.0 Hz, 4F, SF₄), −99.80(t, J=26.0 Hz, 2F, o-F), −100.35 (s, 1F, p-F); ¹H NMR (CDCl₃) δ 6.79 (t,J=17.5 Hz, m-H); ¹³C NMR (CDCl₃) δ 164.16 (dt, J=164.2 Hz, 15.2 Hz,4-C), 158.18 (dm, J=260.7 Hz, 2-C), 127.7 (m, 1-C), 102.1 (tm, J=27.8Hz, 3-C). Elemental analysis; calcd for C₆H₂ClF₇S; C, 26.24%; H, 0.73%.Found, C, 26.23%; H, 1.01%. The NMR shows that2,4,6-trifluorophenylsulfur chlorotetrafluoride obtained is a transisomer.

2,4,6-Trifluorophenylsulfur pentafluoride and3-chloro-2,4,6-trifluorophenylsulfur pentafluoride: The product (b.p.˜145° C.) obtained from Experiment 9 was a 3:1 (molar ratio) mixture of2,4,6-trifluorophenylsulfur pentafluoride and3-chloro-2,4,6-trifluorophenylsulfur pentafluoride. These products wereidentified by NMR and GC-Mass analysis. 2,4,6-Trifluorophenylsulfurpentafluoride: ¹⁹F NMR (CDCl₃) δ 78.7-75.3 (m, SF), 73.8-72.9 (m, SF₄),−100.6 (m, 4-F), −100.7 (m, 2,6-F); ¹H NMR (CDCl₃) δ 6.80 (t, J=8.6 Hz,3,5-H); GC-Mass m/z 258 (M⁺). 3-Chloro-2,4,6-trifluorophenylsulfurpentafluoride: ¹⁹F NMR (CDCl₃) δ 78.7-75.3 (m, SF), 73.8-72.9 (m, SF₄),−101.3 (m, 2 or 6-F), −102.3 (m, 4-F), −102.6 (m, 2 or 6-F); ¹H NMR(CDCl₃) δ 6.95 (br.t, J=9.5 Hz, 5-H); GC-Mass m/z 294, 292 (M⁺).

2,3,4,5,6-Pentafluorophenylsulfur chlorotetrafluoride: The product (b.p.95-112° C./100 mmHg) obtained from Experiment 10 was a 1.7:1 mixture oftrans and cis isomers of 2,3,4,5,6-pentafluorophenylsulfurchlorotetrafluoride. The isomers were assigned by ¹⁹F NMR: The transisomer; ¹⁹F NMR (CDCl₃) δ 144.10 (t, J=26.0 Hz, 4F, SF₄), −132.7 (m, 2F,2,6-F), −146.6 (m, 1F, 4-F), −158.9 (m, 2F, 3,5-F); ¹³C NMR (CDCl₃) δ143.5 (dm, J=265.2 Hz), 141.7 (dm, J=263.7 Hz), 128.3 (m). The cisisomer; ¹⁹F NMR (CDCl₃) δ 152.39 (quartet, J=158.9 Hz, 1F, SF), 124.32(m, 2F, SF₂), 79.4 (m, 1F, SF), −132.7 (m, 2F, 2,6-F), −146.6 (m, 1F,4-F), −158.9 (m, 2F, 3,5-F). High resolution mass spectrum of a 1.7:1mixture of the trans and cis isomers; found 311.923124 (15.5%) (calcdfor C₆ ³⁷ClF₉S; 311.923604), found 309.926404 (43.1%) (calcd for C₆³⁵ClF₉S; 309.926554).

2,3,4,5,6-Pentafluorophenylsulfur pentafluoride: b.p. 135-137° C.; ¹⁹FNMR (CDCl₃) δ 74.8 (m, 5F, SF₅), −133.4 (m, 2F, 2,6-F), −146.2 (m, 1F,4-F), −158.6 (m, 2F, 3,5-F); ¹³C NMR (CDCl₃) δ 143.6 (dm, J=262.2 Hz),137.9 (dm, J=253.6 Hz), 126.7 (m). High resolution mass spectrum; found293.956492 (calcd for C₆F₁₀S; 293.956104).

Example 11 Synthesis of Phenylsulfur Pentafluoride from DiphenylDisulfide with a Mixture of Hydrogen Fluoride and Pyridine as a FluorideSource in Process II

(Process I) Phenylsulfur chlorotetrafluoride was prepared in a highyield in the same manner as in Process I in Example 1.

(Process II) A reaction vessel made of fluoropolymer was charged with341 mg (1.54 mmol) of trans-phenylsulfur chlorotetrafluoride, and 0.5 mLof a mixture of about 70 wt % hydrogen fluoride and about 30 wt %pyridine was added at room temperature. The reaction mixture was stirredat room temperature for 1 hour and heated at 50° C. for 3 hours. Afterthe reaction, the reaction mixture was cooled to room temperature. Ananalysis of the reaction mixture by ¹⁹F-NMR showed that phenylsulfurpentafluoride was produced in 93% yield.

Example 12 Synthesis of Phenylsulfur Pentafluoride from Thiophenol as anAryl Sulfur Compound of Formula (IIb)

(Process I) Chlorine (Cl₂) was passed with a flow rate of 27 mL/min intoa stirred mixture of 10.0 g (90.8 mmol) of thiophenol and 47.5 g (0.817mol) of dry KF in 100 mL of dry acetonitrile at 6˜10° C. Chlorine waspassed for 3.7 h and the total amount of chlorine passed was 10.2 L(0.445 mol). After 10 mL of 1,1,2-trichlorotrifluoroethane was added tothe reaction mixture, the reaction mixture was filtered. After removalof the solvent in vacuum, phenylsulfur chlorotetrafluoride (16.6 g, 83%)as a light green-brown liquid was obtained. The physical properties andspectral data of the product are shown in Example 1. The product was atrans isomer.

(Process II) Phenylsulfur chlorotetrafluoride obtained in Process Iabove may be allowed to react with ZnF₂ in the same procedure as ProcessII in Example 1, giving phenylsulfur pentafluoride in good yield.

Example 13 Synthesis of p-Nitrophenylsulfur Pentafluoride fromp-Nitrobenzenesulfenyl Chloride as an Aryl Sulfur Compound of Formula(IIb)

(Process I) Chlorine (Cl₂) was passed with a flow rate of 37 mL/min intoa stirred mixture of 5.00 g (26.4 mmol) of p-nitrobenzenesulfenylchloride and 15.3 g (264 mmol) of dry KF in 40 mL of dry acetonitrile at5˜11° C. The total amount of chlorine passed was 2.54 L (113 mmol).After 5 mL of 1,1,2-trichlorotrifluoroethane was added to the reactionmixture, the reaction mixture was filtered. After removal of the solventin vacuum, p-nitrophenylsulfur chlorotetrafluoride (4.69 g, 76%) as asolid was obtained. The physical properties and spectral data of theproduct are shown in Example 7. The product was a trans isomer.

(Process II) p-Nitrophenylsulfur chlorotetrafluoride obtained in ProcessI above may be allowed to react with ZnF₂ in the same procedure asProcess II in Example 7, giving p-nitrophenylsulfur pentafluoride ingood yield.

Example 14 Synthesis of Phenylsulfur Pentafluoride from PhenylsulfurTrifluoride

(Process III) Chlorine (Cl₂) was passed with a flow rate of 34 mL/mininto a stirred mixture of 5.00 g (30.1 mmol) of phenylsulfur trifluorideand 8.74 g (150 mmol) of dry KF in 20 mL of dry acetonitrile at 6˜9° C.Chlorine was passed for 43 min and the total amount of chlorine passedwas 1.47 L (65.5 mmol). After 3 mL of 1,1,2-trichlorotrifluoroethane wasadded to the reaction mixture, the reaction mixture was filtered. Afterremoval of the solvent in vacuum, phenylsulfur chlorotetrafluoride (5.62g, 84%) as a colorless liquid was obtained. The physical properties andspectral data of the product are shown in Example 1. The product was atrans isomer.

(Process II) Phenylsulfur chlorotetrafluoride obtained in Process IIIabove may be allowed to react with ZnF₂ in the same procedure as ProcessII in Example 1, giving phenylsulfur pentafluoride in good yield.

Example 15 Reaction of Phenylsulfur Chlorotetrafluoride and ZnF₂ Under aSlow Flow of Chlorine (Presence of Halogen)

(Process II′) trans-Phenylsulfur chlorotetrafluoride (trans-PhSF₄Cl)used for this Process was prepared in high yields by the Process I orIII as shown by Examples 1, 11, 12, or 14. In a dry box, a 50 mLreaction vessel made of fluoropolymer was charged with 10.0 g (0.045mol) of trans-PhSF₄Cl and 2.8 g (0.027 mol) of dry ZnF₂. The reactionvessel was brought out from the dry box and connected to the gas flowingsystem. The reaction mixture was slowly heated to 120° C. while Cl₂ gaswas added into the reaction vessel at the rate of 4.6 mL/minute. Theprogress of the reaction was monitored by ¹⁹F NMR. After 40 minutes at120° C., three major compounds (trans-PhSF₄Cl, cis-PhSF₄Cl, andphenylsulfur pentafluoride (PhSF₅)) were detected to be present in thereaction mixture. The mol ratio of trans-PhSF₄Cl:cis-PhSF₄Cl:PhSF₅ was0.5:3.3:100. After additional 60 minutes at 120° C., trans- andcis-PhSF₄Cl disappeared and only PhSF₅ was detected from ¹⁹F NMR. Thereaction was completed within 1.7 h at 120° C. After N₂ (5.4 mL/minute)was flowed for 0.5 hour, the examination of the reaction mixture by ¹⁹FNMR using benzotrifluoride as a standard showed that phenylsulfurpentafluoride was produced in 92% yield. This experiment showed that thereaction is greatly accelerated by the presence of chlorine and theproduct is obtained in a high yield. This experiment also showed thatcis-PhSF₄Cl is formed intermediately by the isomerization oftrans-PhSF₄Cl, and cis-PhSF₄Cl is converted to the product, PhSF₅.

Example 16 Reaction of Phenylsulfur Chlorotetrafluoride and ZnF₂ Under aFast Flow of Chlorine (Presence of Halogen)

(Process II′) trans-Phenylsulfur chlorotetrafluoride (trans-PhSF₄Cl)used for this Process was prepared in high yields by the Process I orIII as shown by Examples 1, 11, 12 or 14. In a dry box, a 50 mL reactionvessel made of fluoropolymer was charged with 10.0 g (0.045 mol) oftrans-PhSF₄Cl and 2.8 g (0.027 mol) of dry ZnF₂. The reaction vessel wasbrought out from the dry box and connected to the gas flowing system.The reaction mixture was slowly heated to 120° C. while Cl₂ gas wasadded into the reaction vessel at the rate of 23 mL/minute. The progressof the reaction was monitored by ¹⁹F NMR. After 45 minutes at 120° C.,three major compounds (trans-PhSF₄Cl, cis-PhSF₄Cl, and phenylsulfurpentafluoride (PhSF₅)) were detected to be present in the reactionmixture. The mol ratio of trans-PhSF₄Cl:cis-PhSF₄Cl:PhSF₅ was 18:83:100.After additional 45 minutes at 120° C., trans- and cis-PhSF₄Cldisappeared and only PhSF₅ was detected from ¹⁹F NMR. The reaction wascompleted in about 1.5 h at 120° C. After N₂ (26.9 mL/minute) was flowedfor 1 hour, the examination of the reaction mixture by ¹⁹F NMR usingbenzotrifluoride as a standard showed that phenylsulfur pentafluoridewas produced in 83% yield. This experiment showed that the reaction isgreatly accelerated by the presence of chlorine and the product isobtained in a high yield. This experiment clearly showed thatcis-PhSF₄Cl is formed intermediately by the isomerization oftrans-PhSF₄Cl, and cis-PhSF₄Cl is converted to the product, PhSF₅.

Example 17 Reaction of 2,6-Difluorophenylsulfur Chlorotetrafluoride andZnF₂ Under a Flow of Chlorine (Presence of Halogen)

(Process II′) A 6:1 mixture of trans and cis-2,6-difluorophenylsulfurchlorotetrafluoride used for this Process was prepared in high yields bythe Process I or III as shown by Examples 8. In a dry box, a 100 mLreaction vessel made of fluoropolymer was charged with 13.03 g (0.126mol) of dry ZnF₂. The reaction vessel was brought out from the dry boxand connected to the gas flowing system. After nitrogen purge, Cl₂ gasstarted to flow into the reaction vessel at the rate of 15 mL/minute asthe reaction vessel was heated to 130-140° C., at which point additionof 32.36 g (0.126 mol) of the mixture of trans- andcis-2,6-difluorophenylsulfur chlorotetrafluoride was started. A total of32.36 g (0.126 mol) of the mixture of trans- andcis-2,6-difluorophenylsulfur chlorotetrafluoride was added over 1 h.After this, heat and chlorine flow were maintained for an additional 3hours. At this point, the NMR analysis of the reaction mixture showedthat the starting materials (trans- and cis-2,6-difluorophenylsulfurchlorotetrafluoride) were consumed and 2,6-difluorophenylsulfurpentafluoride and 3-chloro-2,6-difluorophenylsulfur pentafluoride wereproduced in 63:37 molar ratio. The reaction mixture was then extractedwith pentane and washed with aqueous sodium carbonate solution. Theextract was dried with dry Na₂SO₄, filtered, and concentrated to give aresidue which was distilled at reduced pressure to give four fractionsof the product in the range of boiling point 75˜120° C. at 110 mmHg. Thefirst three fractions (total 15.37 g) was a 1:1 mixture (by GC) of2,6-difluorophenylsulfur pentafluoride and3-chloro-2,6-difluorophenylsulfur pentafluoride. The final fraction (thefourth fraction, b.p. 112-120° C./110 mmHg) had 6.22 g of3-chloro-2,6-difluorophenylsulfur pentafluoride (93% purity, determinedby GC). The spectral data of 3-chloro-2,6-difluorophenylsulfurpentafluoride were as follows; ¹⁹F NMR (CDCl₃) δ 77.9-75.7 (m, 1F, SF),73.2-72.5 (m, 4F, SF₄), −103.3 (m, 1F), −105.2 (m, 1F); ¹H NMR (CDCl₃) δ7.60 (m, 1H), 7.04 (m, 1H); high resolution mass spectrum, found275.942071 (36.0%) (calcd for C₆H₂ ³⁷ClF₇S; 275.942447), found273.945943 (100%) (calcd for C₆H₂ ³⁵ClF₇S; 273.945397). The otherproduct, 2,6-difluorophenylsulfur pentafluoride was identified by thedata obtained by Example 8 (Process II).

Example 18 Reaction of Phenylsulfur Chlorotetrafluoride and ZnF₂ Under aSlow Flow of an Inactive Gas (Nitrogen)

(Process II) trans-Phenylsulfur chlorotetrafluoride (trans-PhSF₄Cl) usedfor this Process was prepared in high yields by the Process I or III asshown by Examples 1, 11, 12 or 14. In a dry box, a 50 mL reaction vesselmade of fluoropolymer was charged with 10.0 g (0.045 mol) oftrans-PhSF₄Cl and 2.8 g (0.027 mol) of dry ZnF₂. The reaction vessel wasbrought out from the dry box and connected to the gas flowing system.The reaction mixture was slowly heated to 120° C. with N₂ flowing at therate of 5.4 mL/minute. The reaction mixture changed from colorless tolight yellow, to pink, and eventually to brown in about 30 minutes. Thereaction mixture was stirred at 120° C. with N₂ flowing for 5 hours.After being cooled down to room temperature, the reaction mixture waschecked with ¹⁹F NMR. Three major compounds (trans-PhSF₄Cl, cis-PhSF₄Cland PhSF₅) were present in the reaction mixture. The ratio oftrans-PhSF₄Cl:cis-PhSF₄Cl:PhSF₅ was 15:20:100. PhCF₃ (1.0 g) was addedto the reaction mixture and the NMR yield of each compound wasdetermined. The yield of trans-PhSF₄Cl was 2.4%, cis-PhSF₄Cl was 14.6%,and PhSF₅ was 67.2%. The reaction was not complete in 5 h at 120° C.Therefore, this experiment showed that the reaction under the flow ofnitrogen was slowed down.

Example 19 Reaction of Phenylsulfur Chlorotetrafluoride and ZnF₂ Under aFast Flow of Inactive Gas (Nitrogen)

(Process II) trans-Phenylsulfur chlorotetrafluoride (trans-PhSF₄Cl) usedfor this Process was prepared in high yields by Process I or III asshown by Examples 1, 11, 12 or 14. In a dry box, a 50 mL reaction vesselmade of fluoropolymer was charged with 10.0 g (0.045 mol) oftrans-PhSF₄Cl and 2.8 g (0.027 mol) of dry ZnF₂. The reaction vessel wasbrought out from the dry box and connected to the gas flowing system.The reaction mixture was slowly heated to 120° C. with N₂ flowing at arate of 26.9 mL/minute. The reaction mixture changed from colorless tolight yellow, to pink, and eventually to brown in about 30 minutes. Thereaction mixture was stirred at 120° C. with N₂ flowing for 5 hours.After being cooled down to room temperature, the reaction mixture waschecked with ¹⁹F NMR. Three major compounds (trans-PhSF₄Cl, cis-PhSF₄Cland PhSF₅) were present in the reaction mixture. The ratio oftrans-PhSF₄Cl:cis-PhSF₄Cl:PhSF₅ was 22:117:100. PhCF₃ (2.8 g) was addedto the reaction mixture and the NMR yield of each compound wasdetermined by ¹⁹F NMR. The yield of trans-PhSF₄Cl was 6.7%, cis-PhSF₄Clwas 42.1%, and PhSF₅ was 38.4%. The reaction was not complete in 5 h at120° C. and the conversion of PhSF₄Cl to PhSF₅ was lower than in Example18. This reaction showed that the reaction under the fast flow ofnitrogen was slowed down more than the reaction under the slow flow ofnitrogen. In either case a flow of inactive gas has an inhibitory effecton reaction yield.

Example 20 Synthesis of Phenylsulfur Pentafluoride by Using SbF₃ as aFluoride Source

(Process II) trans-Phenylsulfur chlorotetrafluoride used for thisProcess was prepared in high yields by the Process I or III as shown byExamples 1, 11, 12, or 14. In a dry box, a reaction vessel made offluoropolymer was charged with 1.0 g (4.54 mmol) of trans-phenylsulfurchlorotetrafluoride and 0.397 g (2.22 mmol) of dry SbF₃. The reactionvessel was brought out from the dry box and equipped with a balloonfilled with N₂. The mixture was stirred at 80° C. for 5 h. The analysisof the reaction mixture by ¹⁹F-NMR technique showed that phenylsulfurpentafluoride was produced in 33% yield.

Example 21 Synthesis of Phenysulfur Pentafluoride by Using a Mixture ofSbF₃ (Fluoride Source) and SbCl₅ (Fluoride Source-Activating Compound)as a Fluoride Source

(Process II) trans-Phenylsulfur chlorotetrafluoride used for thisProcess was prepared in high yields by the Process I or III as shown byExamples 1, 11, 12, or 14. In a dry box, a reaction vessel made offluoropolymer was charged with 1.0 g (4.54 mmol) of trans-phenylsulfurchlorotetrafluoride, 0.349 g (2.01 mmol) of SbF₃, a trace amount ofSbCl₅, and 2 mL of dry hexane. SbCl₅ is a fluoride source-activatingcompound. SbCl₅ (strong Lewis acid) can complex with SbF₃ to formSbF₂(SbFCl₅), which can also be made by SbF₂Cl and SbFCl₄ both arefluoride sources usable in this invention. The reaction vessel wasbrought out from the dry box and equipped with a balloon filled with N₂.The mixture was stirred at room temperature for 3 days. The analysis ofthe reaction mixture by ¹⁹F-NMR showed that phenylsulfur pentafluoridewas produced in 54% yield.

Example 22 Synthesis of Phenylsulfur Pentafluoride by Using SnF₄ as aFluoride Source

(Process II) trans-Phenylsulfur chlorotetrafluoride used for thisProcess was prepared in high yields by the Process I or III as shown byExamples 1, 11, 12, or 14. In a box, a reaction vessel made offluoropolymer was charged with 1.0 g (4.54 mmol) of trans-phenylsulfurchlorotetrafluoride and 0.26 g (1.4 mmol) of dry SnF₄. The reactionvessel was brought out from the dry box and equipped with a balloonfilled with N₂. The mixture was stirred at 80° C. for 2 h. The analysisof the reaction mixture by ¹⁹F-NMR showed that phenylsulfurpentafluoride was produced in 34% yield.

Example 23 Synthesis of Phenylsulfur Pentafluoride by Using TiF₄ as aFluoride Source

(Process II) trans-Phenylsulfur chlorotetrafluoride used for thisProcess was prepared in high yields by the Process I or III as shown byExamples 1, 11, 12, or 14. In a dry box, a reaction vessel made offluoropolymer was charged with 1.0 g (4.54 mmol) of trans-phenylsulfurchlorotetrafluoride and 0.17 g (1.4 mmol) of dry TiF₄. The reactionvessel was brought out from the dry box and equipped with a balloonfilled with N₂. The mixture was stirred at 80° C. for 16 h. The analysisof the reaction mixture by ¹⁹F-NMR showed that phenylsulfurpentafluoride was produced in 35% yield.

Example 24 Synthesis of Phenylsulfur Chlorotetrafluoride from DiphenylDisulfide

(Process I) A 500 mL round bottom flask was charged with diphenyldisulfide (21.8 g, 0.1 mol), dry CsF (243.2 g, 1.6 mol) and 200 mL ofdry CH₃CN. The reaction mixture was cooled on an ice/water bath, andbubbled with N₂ (18 mL/min) for 0.5 h. After the N₂ flow was stopped,Cl₂ was bubbled into a reaction mixture at the rate of 63 mL/min for 4h. The total amount of Cl₂ used was 0.68 mol. The reaction mixture wasthen warmed to room temperature and stirred overnight. Then, N₂ (18mL/min) was bubbled through for 2 hours to remove an excess of chlorine.The reaction mixture was filtered with 100 mL of dry hexanes in a drybox. The combined filtrate was evaporated under vacuum, and the residuewas distilled at reduced pressure to give a colorless liquid ofphenylsulfur chlorotetrafluoride (36.3 g, 83%). The physical propertiesand spectral data of the product are shown in Example 1. The product wasa trans isomer.

Example 25 Synthesis of p-Chlorophenylsulfur Chlorotetrafluoride fromBis(p-Chlorophenyl) Disulfide

(Process I) Chlorine (Cl₂) was passed with a flow rate of 64 mL/min intoa stirred mixture of 25.0 g (87.0 mmol) of bis(p-chlorophenyl)disulfideand 86.0 g (1.48 mol) of dry KF in 200 mL of dry acetonitrile at 5-8° C.Chlorine was passed for 3.5 h and the total amount of chlorine passedwas 12.8 L (571 mmol). After that, the reaction mixture was filtered andrinsed with dry hexane. After removal of the solvent in vacuum,p-chlorophenylsulfur chlorotetrafluoride (39.5 g, 88%) as a colorlessliquid was obtained; b.p. 65-66° C./2 mmHg; ¹H NMR (CDCl₃) δ 7.38 (d,2H, J=9.1 Hz), 7.65 (d, 2H, J=9.1 Hz); ¹⁹F NMR (CDCl₃) 137.4 (s, 4F,SF₄Cl). High resolution mass spectrum; found 257.927507 (13.3%) (calcdfor C₆H₄F₄S³⁷Cl₂; 257.928790), found 255.930746 (68.9%) (calcd forC₆H₄F₄S³⁷Cl³⁵Cl; 255.931740), found 253.933767 (100.0%) (calcd forC₆H₄F₄S³⁵Cl₂; 253.934690). The NMR showed that p-chlorophenylsulfurchlorotetrafluoride obtained is a trans isomer.

Example 26 Synthesis of p-(Tert-Butyl)Phenylsulfur Chlorotetrafluoridefrom p-(Tert-Butyl)Benzenethiol

(Process I) Chlorine (Cl₂) was passed with a flow rate of 35 mL/min intoa stirred mixture of 10.0 g (60.2 mmol) of p-(tert-butyl)benzenethioland 91.6 g (602 mmol) of dry CsF in 150 mL of dry acetonitrile at 5˜10°C. Chlorine was passed for 3.5 h and the total amount of chlorine passedwas 10.1 L (452 mmol). After that, the reaction mixture was stirred atroom temperature for 24 h. The reaction mixture was filtered under drynitrogen. After removal of the solvent at reduced pressure, the residuewas distilled to give 14 g (84%) of p-(tert-butyl)phenylsulfurchlorotetrafluoride; b.p. 98° C./0.3 mmHg; m.p. 93° C.; ¹H NMR (CDCl₃) δ1.32 (s, 9H, C(CH₃)₃), 7.43 (d, J=9.2 Hz, 2H, aromatic), 7.64 (d, J=9.2Hz, 2H, aromatic); ¹⁹F NMR δ 138.3 (s, SF₄Cl). High resolution massspectrum; found 278.034576 (8.8%) (calcd for C₁₀H₁₃ ³⁷ClF₄S;278.033313), found 276.037526 (24.7%) (calcd for C₁₀H₁₃ ³⁵ClF₄S;276.036263). Elemental analysis; Calcd for C₁₀H₁₃ClF₄S; C, 43.40%; H,4.74%. Found; C, 43.69%, H, 4.74%. The NMR showed thatp-(t-butyl)phenylsulfur chlorotetrafluoride was obtained as a transisomer.

Example 27 Synthesis of Phenylsulfur Pentafluoride from PhenylsulfurChlorotetrafluoride and ZnF₂

(Process II or II″) In a dry box, a reaction vessel made offluoropolymer was charged with 1.0 g (4.54 mmol) of trans-phenylsulfurchlorotetrafluoride and 0.281 g of dry ZnF₂ (solid, mp 872° C., bp 1500°C.). The reaction vessel was brought out from the dry box and equippedwith a balloon filled with N₂. The mixture was heated at 80° C. for 20h. An analysis of the reaction mixture by ¹⁹F-NMR showed thatphenylsulfur pentafluoride was produced in 85% yield.

Example 28 Synthesis of Phenylsulfur Pentafluoride from PhenylsulfurChlorotetrafluoride and ZnF₂

(Process II or II″) In a dry box, a reaction vessel made offluoropolymer was charged with 1.0 g (4.54 mmol) of trans-phenylsulfurchlorotetrafluoride and 0.28 g (2.7 mmol) of dry ZnF₂ (solid, mp 872°C., bp 1500° C.). The reaction vessel was brought out from the dry boxand equipped with a balloon filled with N₂. The mixture was heated at120° C. for 4 h. An analysis of the reaction mixture by ¹⁹F-NMR showedthat phenylsulfur pentafluoride was produced in 88% yield.

Example 29 Synthesis of Phenylsulfur Pentafluoride from PhenylsulfurChlorotetrafluoride and CuF₂

(Process II or II″) In a dry box, a reaction vessel made offluoropolymer was charged with 1.0 g (4.54 mmol) of trans-phenylsulfurchlorotetrafluoride and 0.284 g (2.79 mmol) of dry CuF₂ (solid, mp ˜785°C.). The reaction vessel was brought out from the dry box and equippedwith a balloon filled with N₂. The mixture was heated at 80° C. for 22h. An analysis of the reaction mixture by ¹⁹F-NMR showed thatphenylsulfur pentafluoride was produced in 57% yield.

Example 30 Synthesis of p-Methylphenylsulfur Pentafluoride fromp-Methylphenylsulfur Chlorotetrafluoride and ZnF₂

(Process II or II″) In a dry box, a reaction vessel made offluoropolymer was charged with 1.01 g (4.26 mmol) oftrans-p-methylphenylsulfur chlorotetrafluoride and 0.266 g (2.57 mmol)of dry ZnF₂ (solid, mp 872° C., bp 1500° C.). The reaction vessel wasbrought out from the dry box and equipped with a balloon filled with N₂.The mixture was heated at 80° C. for 16 h. An analysis of the reactionmixture by ¹⁹F-NMR showed that p-methylphenylsulfur pentafluoride wasproduced in 79% yield.

Example 31 Synthesis of Phenylsulfur Pentafluoride from PhenylsulfurChlorotetrafluoride and HBF₄ Diethyl Etherate

(Process II or II″) In a dry box, a reaction vessel made offluoropolymer was charged with 1.0 g (4.5 mmol) of trans-phenylsulfurchlorotetrafluoride (trans-PhSF₄Cl) and 4.5 mL of dry methylenechloride. The reaction vessel was brought out from the dry box andequipped with a balloon filled with nitrogen. Into the solution, HBF₄diethyl etherate (liquid) (HBF₄OEt₂) (0.88 g, 0.74 mL, 5.4 mmol) wasslowly added. The reaction mixture was stirred at room temperature. Theprogress of the reaction was monitored by ¹⁹F NMR. After 7 hours, threemajor compounds (trans-PhSF₄Cl, cis-PhSF₄Cl and PhSF₅) were present inthe reaction mixture. The ratio of trans-PhSF₄Cl:cis-PhSF₄Cl:PhSF₅ was156:716:100. After 21 hours, the ratio oftrans-PhSF₄Cl:cis-PhSF₄Cl:PhSF₅ changed to 3:6:100. An analysis of thereaction mixture by ¹⁹F-NMR showed that phenylsulfur pentafluoride(PhSF₅) was produced in 40% yield.

Example 32 Synthesis of Phenylsulfur Pentafluoride from PhenylsulfurChlorotetrafluoride by Using a Mixture of ZnF₂ (Fluoride Source) andSbCl₅ (Fluoride Source-Activating Compound) as a Fluoride Source

In a dry box, a reaction vessel made of fluoropolymer was charged withdry heptane (5 mL) and ZnF₂ (solid) (0.84, 8.2 mmol), SbCl₅ (liquid)(0.41 g, 0.17 mL, 1.36 mmol) was added into the mixture. To this,trans-phenylsulfur chlorotetrafluoride (trans-PhSF₄Cl) (3.0 g, 13.6mmol) was slowly added. The reaction vessel was brought out from the drybox and equipped with a balloon filled with nitrogen. SbCl₅ is afluoride source-activating compound. SbCl₅ (strong Lewis acid) cancomplex with ZnF₂ to form ZnF(SbFCl₅), which can also be made by ZnFCland SbFCl₄ both are fluoride sources usable in this invention. Thereaction mixture was stirred at room temperature. The progress of thereaction was monitored by ¹⁹F NMR. After 10 minutes, the ratio oftrans-PhSF₄Cl:cis-PhSF₄Cl:PhSF₅ was 385:0:100. After 90 minutes, theratio of trans-PhSF₄Cl:cis-PhSF₄Cl:PhSF₅ changed to 63:trace:100. After180 minutes, the ratio of trans-PhSF₄Cl:cis-PhSF₄Cl:PhSF₅ changed to34:trace:100. After 17 hours, the ratio oftrans-PhSF₄Cl:cis-PhSF₄Cl:PhSF₅ changed to 18:2:100. An analysis of thereaction mixture by ¹⁹F-NMR showed that phenylsulfur pentafluoride(PhSF₅) was produced in 53% yield. A small amount of the startingtrans-PhSF₄Cl (9.4%) remained.

Example 33 Reaction of Phenylsulfur Chlorotetrafluoride and BF₃ Gas(Comparative Example)

A reaction vessel made of steel was charged with 1.0 g (4.5 mmol) oftrans-phenylsulfur chlorotetrafluoride and cooled on a dry ice-acetonebath. The reaction vessel was evacuated by a vacuum pump and borontrifluoride gas (BF₃; this boiling point is −100° C. at 1 atm) wasintroduced into the reaction vessel till the pressure reached 18 psi.The reaction mixture was then warmed to room temperature and stood for 3days. During the time, the pressure was increased to 100 psi withadditional BF₃ gas. After the reaction, it was found that all thereaction mixture became a solid residue. Phenylsulfur pentafluoride wasnot detected.

Example 34 Reaction of Phenylsulfur Chlorotetrafluoride and BF₃ Gas inMethylene Chloride (Comparative Example)

A reaction vessel made of steel was charged with 1.42 g (6.44 mmol) oftrans-phenylsulfur chlorotetrafluoride and 6.4 mL of dry methylenechloride and cooled to about −100° C. by using a liquid nitrogen bath.The reaction vessel was evacuated by a vacuum pump and BF₃ gas (boilingpoint is −100° C. at 1 atm) was introduced into the reaction vessel tillthe pressure reached 80 psi. The reaction mixture was warmed to roomtemperature and stood for 5 h. During this time, the pressure wasincreased to 100 psi with additional BF₃ gas. An analysis of thereaction mixture by ¹⁹F-NMR showed that phenylsulfur pentafluoride wasformed in 28% yield.

Examples 33 and 34 show that as Ou et al. reported, it was found that,when boron trifluoride (boiling point −100° C. at 1 atm) was flowedthrough a solution of phenylsulfur chlorotetrafluoride in a deuteriummethylene chloride, phenylsulfur chlorotetrafluoride was slowlytransferred to phenylsulfur pentafluoride (see Can. J. Chem., Vol. 75,pp. 1878-1884). As shown herein, however, the yield was very low or thedesired product was not obtained because an undesired polymerizationoccurred. Examples 33 and 34 show the utility of the present inventionover the conventional art production method using a fluoride gas such asboron trifluoride whose boiling point is −100° C. at 1 atm. The presentinvention preferably uses fluoride liquids or solids at least at 0° C.and at 1 atm, as compared to a gaseous reactant. A liquid or solid ispreferable because it is easy to handle and reacts more completely thana gaseous reactant. Also, the reactant of Ou et al., although shown toreact at atmospheric pressure, would require high pressure to proceed atan appreciable rate with a necessary and minimum amount of the reactant.

While the invention has been particularly shown and described withreference to a number of embodiments, it would be understood by thoseskilled in the art that changes in the form and details may be made tothe various embodiments disclosed herein without departing from thespirit and scope of the invention and that the various embodimentsdisclosed herein are not intended to act as limitations on the scope ofthe claims.

1. A fluorinated arylsulfur pentafluoride of2,3,4,5,6-pentafluorophenylsulfur pentafluoride.